TWI265976B - Ag base alloy thin film and sputtering target for forming Ag base alloy thin film - Google Patents

Abstract

The present invention relates to an Ag alloy film. Particularly, it is preferably used as a reflective film or semi-transmissive reflective film for an optical information recording medium having high thermal conductivity/high reflectance/high durability in the field of optical information recording media, an electromagnetic-shielding film excellent in Ag aggregation resistance, and an optical reflective film on the back of a reflection type liquid crystal display device, or the like. The Ag alloy film of the present invention comprises an Ag base alloy containing Bi and/or Sb in a total amount of 0.005 to 10% (in terms of at%). Further, the present invention relates to a sputtering target used for the deposition of such an Ag alloy film.

Description

1265976 (1) EMBODIMENT OF THE INVENTION [Technical Field] The present invention relates to an Ag alloy film, which is particularly suitable for use in optical information recording media, and has optical information recording with high thermal conductivity, high reflectivity, and high durability. A reflective film for a medium, a semi-transmissive reflective film, an electromagnetic wave shielding film excellent in Ag aggregation resistance, or an optical reflection film on the back surface of a reflective liquid crystal display element or the like. The invention further relates to a sputtering target for depositing the Ag alloy film. [Prior Art] In a reflective film or a semi-transmissive reflective film of an optical information recording medium (disc), Au, Al, Ag, or a combination thereof has been widely used from the viewpoint of thermal conductivity 'reflectance and durability. The alloy of the main ingredients. Ag-based reflective film containing Ag as a main component has high thermal conductivity for high-reflectivity for blue-violet lasers for next-generation optical discs, writeable/rewriteable discs, and raw material costs lower than Au The characteristic of the underlying reflective film is therefore a material that is promising as a reflective film or a semi-transmissive reflective film. However, from the viewpoint of durability, although it is superior to the A1 substrate reflective film, it does not have high durability comparable to that of the Au substrate reflective film. In order to actually be a reflective film or a semi-transmissive reflective film of an optical disk, it is necessary to improve durability without damaging the high reflectance and high thermal conductivity of Ag. For such a method of improving the durability of the Ag substrate reflective film, the following improved method has been reported. For example, according to U.S. Patent No. 6007889, by adding a force to Au, Pd, Cu, Rh, Ru, Os, Ir, and Pt, or (2) (2)

1265976 According to U.S. Patent No. 5,948,497, Pd is added to Ag to individually improve durability (chemical stability). In addition, Japanese Laid-Open Patent Publication No. 2002-15524 refers to a method of improving durability (inhibition of crystal grain growth, etc.) by using an Ag earth metal element. However, in high-speed recording DVDs or next-generation optical discs, the required characteristics of the film are further improved, requiring higher levels of conductivity, thermal conductivity, and reflectance than at present. Especially regarding durability, the S property of a halogen element including chlorine is required. This requirement is inconvenient for a write-once optical disc in which an organic dye recording film containing a halogen element, a protective layer, and the like are directly laminated with a reflective film. Further, the next-generation optical disc differs from the DVD in that it has a reverse laminated configuration prepared as follows: a film is formed on a transparent plastic substrate, and then a dielectric protective film/recording film/force film is laminated thereon. Therefore, in order to suppress the deterioration of the recording and reproducing characteristics, it is necessary to lower the surface roughness of the reflective film, and it is required to maintain the stability of the surface roughness even under thermal load. Further, it is necessary to rapidly diffuse heat which is generated in the minute region of the recording film by the radium for the thermal conductivity. The reflective film requires a high conductivity to simultaneously function as a thermal diffusion film. Further, the "reflection film" is required to have a high reflectance for the cyan violet laser for recording the next-generation optical disk at a high speed. However, Ag-based alloys that meet all of these requirements are guaranteed to be used as high-speed recording DVDs or next-generation discs and Cu, and are also added to the thin; heat-stable to reflect the durability of the corrosion-resistant enamel film, adhesion In particular, the following squares reflect the reflection ~ the electric body protects the extreme drop f, and can also f-produce the coefficient, DVD or i appears. J Highly Reliable (3) 1265976 Properties 'Ag prime alloys with all the required characteristics such as high thermal conductivity, high reflectivity and high durability are strongly required. On the other hand, the Ag film has been used in various applications due to its high visible light transmittance and excellent infrared ray shielding properties. For example, in order to improve the heating and cooling in the room, the efficiency is formed by sputtering or the like on a transparent substrate such as glass.

The infrared mask of Ag is made of an Ag film transparent body. Further, the Ag film is excellent in radio wave shielding property, for example, in order to protect an electronic device that is erroneously operated by radio waves from external electric waves, or to suppress radio wave radiation generated from an electronic device. The laboratory's window-household-glass application: Ag film, or a built-in or external Ag film or a substrate to which an Ag film is applied. However, the Ag film is inferior in abrasion resistance and has insufficient durability to the environment, so it is deteriorated by moisture or the like, and it is difficult to use it for a long period of time. Therefore, a method of thickening the Ag film is employed. However, from the viewpoint of improving wear resistance and durability, the problem has not been sufficiently solved, and as a result, the Ag film deteriorates with time, and the pure Ag film lacks practicality. Further, although the thick film is improved in electromagnetic wave shielding properties (infrared masking property and radio wave masking property), the visible light transmittance " is reduced, and the room is darkened. Therefore, as a technique for increasing the permeability of the visible light region and improving the wear resistance and weather resistance of the A g film, it is proposed to be composed of an oxide such as tin oxide, zinc oxide, or titanium oxide, or a nitride such as tantalum nitride. A technique of coating a Ag film with a transparent dielectric film. Further, in order to improve the adhesion between the Ag film and these oxides or nitrides, a technique of inserting a Cr or Ni-Cr alloy layer between an Ag film and an oxide or a nitride has been proposed. (4) 1265976 According to this technique, since the light reflectance of the Ag film can be lowered, the blaze caused by the reflected light of the Ag film can be reduced, and an effect longer than the durability of the above pure Ag film can be obtained. However, Ag is coated with a transparent dielectric film. If it is exposed to the atmosphere after film formation, Ag is agglomerated with defects such as pores or scratches of the transparent dielectric film, and it is easy to cause cracking of the Ag film. (ie, the continuity of the film disappears), resulting in a split film. If this is the case (the continuity of the film is lost), the conductivity of the Ag film is lost, and the electromagnetic wave and the mask characteristics are remarkably lowered. And based on Ag agglomeration, glass or film, etc., produces a lot of white spots on the surface of the substrate with the A g film, which reduces the design and commerciality. — As a technique for improving the aggregation of such an Ag film, various different techniques have been proposed. For example, Japanese Patent Laid-Open No. Hei 7- 3 1 5 8 74 / 1 995 has proposed the formation of a 5 g on the surface of a glass plate. 20% by mole of a hot-line mask glass of at least one metal film transported from elements of Pd, Pt, Sη, Ζη, Iη, Cr, Ti, S i, Zr, Nb, Ta. φ In addition, Japanese special Kaiping 8 - 293379/1996 has proposed to laminate a metal layer whose main component is Ag and Pd containing 0.5 to 5 atom% of Ag on a substrate, and the main component is at least one metal oxide selected from Zn, In or Sn. The technique of the dielectric layer is such that the metal layer is interposed between the transparent dielectric layers. - Further, Japanese Patent Laid-Open Publication No. Hei 9-135096/1997 has been proposed.

An electromagnetic wave shielding substrate in which at least one element selected from the group consisting of Pb, Cu, An, Ni, Zn, Cd, Mg, or A1 is added to Ag, and Japanese Patent Laid-Open No. Hei 11-231122/1999 has been proposed by Add 1265976 to Ag (5)

Pb, Cu, Au, Ni, Pd, Pt, Zn, Cd, Mg, and A1 are techniques for improving the agglutination resistance of A g . Further, the present inventors have proposed a technique for improving the agglutination resistance of Ag by adding Sc, Y, and a rare earth 'element element to Ag (Japanese Patent No. 1 3 - 3 5 1 5 72 / 200 No. 1). However, these proposed and proposed Ag alloy films are also pushed over time, which causes Ag to aggregate and deteriorate the Ag alloy film. Therefore, when the surface of the Ag Φ alloy film coating is exposed to the atmosphere, Ag is aggregated around the defect portion of the transparent film covering the Ag alloy film, and as a result, the Ag alloy film surface is not exposed to In the atmosphere, it must be processed into laminated glass or laminated glass to cause an increase in manufacturing costs. Further, even in the case of forming a laminated glass or a laminated glass, if a laminated glass or a laminated glass is not processed immediately after the film formation of Ag, white spots are generated and the use price as a commercial product is lost. Further, even in the case of forming a laminated glass or a laminated glass, if the Ag alloy film is used for a long period of time, it will deteriorate, and thus it is impossible to have sufficient ® durability. Recently, a reflective liquid crystal display element which consumes less power without a built-in lamp has been attracting attention. The back surface of the reflective liquid crystal display element must be provided with a light reflecting film as a reflecting plate, and indoor light or natural light is reflected as a light source for forming an image. Therefore, the higher the reflectance of the light reflecting film, the easier it is to form a bright and clear image. Conventionally, as the light-reflecting film, A1 film having a high reflectance has been used. However, a film (Ag film) of an Ag film having a high reflectance and high chemical resistance has recently been used as a light-reflecting film. -9- (6) 1265976 However, crystallization occurs when the Ag film is exposed to air for a long time at a high temperature during the manufacture of a liquid crystal display element, or exposed to high temperature and high humidity for a long time during use. The whitening or white spots caused by coarsening of the particles, aggregation of Ag atoms, oxidation of Ag, etc., and the reflectance are lowered, so that the high reflectance of Ag is not obtained. Further, depending on the heat history unavoidable in the manufacturing process of the device (to 200 ° C), the formation of the film becomes difficult due to the increase in the roughness of the surface of the film or the growth of the abnormal particles due to the growth of crystal grains or the aggregation of Ag atoms. Or the reflectivity is further reduced. Therefore, in order to prevent the growth of crystal grains of A g or the aggregation of A g atoms, it is proposed to maintain the original high light reflectance of Ag, and it has been proposed to add other kinds of elements in Ag. For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A film composed of a silver alloy (Ag base alloy). In addition, Japanese Laid-Open Patent Publication No. Hei 9-23 0806/1 997 discloses an element of other kinds, which is selected from aluminum, copper, nickel, cadmium, gold, zinc or magnesium, and is resistant to migration of silver. A film composed of a silver-based metal material (Ag-based alloy) of an alloy of two or more kinds of metals. However, the above prior art cannot sufficiently prevent the crystal grains of Ag from being aggregated or Ag atoms, and thus the original high light reflectance of Ag cannot be ensured. SUMMARY OF THE INVENTION -10- 1265976 (7) SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances. Its first objective is to provide high-speed DVD or next-generation optical discs with high reliability by finding Ag-based alloys with high thermal conductivity, high reflectivity, and high durability compared to pure Ag or existing Ag alloys. An Ag-based alloy reflective film or a semi-transmissive reflective film for an optical information recording medium, and an optical information recording medium having the reflective film or the semi-transmissive reflective film. # A second object of the present invention is to provide an Ag alloy film for electromagnetic wave shielding which is less likely to cause aggregation of Ag, and further excellent durability, and an Ag alloy film forming body for electromagnetic wave shielding. The third object of the present invention is to provide a high-light reflection having almost the same high light reflectance as Ag by finding an Ag-based alloy capable of preventing the growth of Ag crystal grains or Ag atoms from being prevented as much as possible. A high-performance light reflecting film or a liquid crystal display element using the light reflecting film. A fourth object of the present invention is to provide a sputtering target which can be used for film formation of the above various Ag alloy ® films. The Ag-based alloy film of the present invention which achieves any of the above objects contains at least one element selected from the group consisting of Bi and Sb, and the total content of Bi and Sb is 0.005 to 10% by atom. The thickness of the Ag-based alloy film is suitably from 3 to 300 nm. Further, in the Ag-based alloy thin film, it is preferable to further contain at least one rare earth metal element which is at least one selected from the group consisting of N d and Y. If the film is composed of Ag-base alloy having a total content of Bi and Sb of 0.005 to 0.40 atom%, the Ag-based alloy film will have a high thermal conductivity, high reflectance, and high. Durability, the first purpose can be achieved. Here, suitably, the Ag-based alloy further contains at least one element selected from the group consisting of Nd and Y, and the total content of the element is 0.1 to 2 atom%. Further, the Ag-based alloy further contains at least one element selected from the group consisting of Cu, Au, Rh_, Pd or Pt, and the total content of the element is 0.1 to 3 atom%. If the film is composed of an Ag-based alloy having a total content of Bi and Sb of 0.01 to 10% by atom, the Ag-based alloy film is less likely to generate Ag aggregation and thus has excellent durability, and the second can be realized. Purpose. Here, suitably, the Ag-based alloy further contains at least one element selected from Cu, Au, Pd, Rh, Ru, Ir or Pt, and the total content of the element is 〇·3 atom% or more. If the film is composed of an Ag-based alloy having a total content of Bi and Sb of 0.01 to 4 atom%, the Ag-based alloy film can prevent crystal grain growth of Ag or aggregation of Ag atoms as much as possible. It also has a high light reflectivity that is almost equal to the original high light reflectance of Ag, and can achieve the third purpose. Here, it is preferable that the Ag-based alloy further contains a rare earth metal element of 1 to 2 atom% of lanthanum cerium, and the rare earth metal element is suitably at least one of N d and Y. At least one of Bi: 〇·05 to 23 at% and sb: 0.005 to 10 at% of the sputtering target for sputtering target formation of the present invention for the purpose of the invention. If the Ag target film forming sputtering target contains 0.05 to 4.5 atom% of Bi or sb containing 5 to 4 atom% of the sputtering target, it is suitable for high thermal conductivity, high reflectance, and high durability. Ag-based alloy thin film -12- 1265976 (9) film formation. - if the content in the sputtering target is at least one of Bi: 0.2 to 23 at% and Sb: 0.0 1 to 10 at%, and the amount of B i and the amount of Sb in the sputtering target satisfy the following formula (1) It is suitable for film formation of an Ag-based alloy thin film which is less likely to cause Ag aggregation and further has excellent durability. 01 Atomic % € 0.0005 02X3 + 0.009 8 7X2 + 0.0 5 5 3 X + y $ 1 0 Atomic % ...... Formula (1 ) ^ In the above formula (1), X is the amount of Bi in the sputtering IE of Ag substrate (Atomic %), yMAg, and the amount of Sb (atomic %) in the beach target. Further, it is preferable to contain at least one element selected from the group consisting of Cu, Au, Pd, Rh, *Ru, Ir or Pt. - if the content in the sputtering target satisfies at least one of Bi: 0.2 to 15 at% and Sb: t 01 to 4 at%, and the amount of Bi and the amount of Sb in the sputtering target satisfy the following formula (2) In addition, it is suitable for the formation of an Ag-based alloy thin film which is capable of preventing the formation of Ag crystals, grain growth, or aggregation of Ag atoms as much as possible, and having a high light reflectance which is almost equal to the Ag light > membrane. 01 Atomic %S 0.0 00502X3 + 0.00987X2 + 0.0553X + y€4 Original - ' Sub% ...... Equation (2) • In the above formula (2), X is the amount of Bi in the Ag alloy sputtering target (Original '%%), 乂 is the amount of Sb (atomic %) in the eight-8 alloy sputtering target.

An Ag-based alloy film having a total content of Bi and Sb of 0.005 to 0.40 atom% is suitably used as a reflective film or a semi-transmissive reflective film for an optical information recording medium. •13- (10) 1265976

The total content of Bi and Sb is (^丨~; ^ atom% of the Ag-based alloy film is suitable for use as an electromagnetic wave mask film, Q in the electromagnetic wave mask film, suitably the surface and interface of the Ag-based alloy film At least one of the layers having at least one of 8 Å and -Sb is more than the inner layer of the Ag-based alloy film. Further, in the electromagnetic wave mask film, a layer having a high content of at least one of B i and S b is suitably used. Containing at least one of Bi oxide and Sb oxide.

The total content of Bi and Sb is Ag·〇ι~10 atom% of Ag substrate. ☆ # Gold film is also suitable as an electromagnetic wave mask film former. The electromagnetic wave mask film forming body may be configured such that a film containing at least one selected from the group consisting of an oxide, a nitrogen compound, or an oxynitride is formed on the substrate as a bottom layer on which the Ag substrate is formed A film is formed on the Ag-base alloy film to form a film containing at least one selected from the group consisting of oxides, nitrides, and oxynitrides as a protective layer. Here, suitably, the underlayer and the protective layer are oxides or oxynitrides. Further, suitably, the oxide is at least one selected from the group consisting of ITO, zinc oxide, tin oxide, and indium oxide. Further, suitably, the underlayer and the protective layer have a thickness of 10 nm or more and 100 nm or less. The electromagnetic wave mask film forming body is suitably configured such that the substrate is a transparent substrate, or a transparent body is laminated on the protective layer, or a transparent body is laminated on the protective layer via a separator, and the protective layer and the protective layer A space layer is provided between the transparent bodies. In the electromagnetic wave mask film forming body, the thickness of the Ag-based alloy film is preferably -3 nm or more and 20 nm or less. -

An Ag-based gold alloy film having a total content of Bi and Sb of 〇·〇1 to 4 at% is suitably used as a light-reflecting film for a reflective electrode or a reflector of a liquid crystal display element. -14- (11) 1265976 When the Ag-based alloy of the present invention is used for a reflective film or a semi-transmissive reflective film for optical information recording media, it has high thermal conductivity, high reflectance, and high durability, and thus can be greatly improved. The recording and reproduction characteristics and reliability of optical information recording media (especially high-speed DVD or next-generation optical discs). Further, the sputtering target for forming an Ag-based alloy thin film of the present invention is suitably used as a reflective film or a semi-transmissive reflective film of an optical information recording medium, and an alloy composition and an alloying element of a reflective film or a semi-transmissive reflective film formed thereon are used. Distribution and • Film thickness is excellent in in-plane uniformity. In addition, since the content of the impurity component of the reflective film or the semi-transmissive reflective film is small, the high performance (high thermal conductivity, high reflectance, and high durability) of the reflective film can be satisfactorily exhibited, and the product can be produced. High performance and highly reliable optical information recording medium. Further, the optical information recording medium having the reflection or the film or the semi-transmissive reflection film can greatly improve the characteristics and reliability of recording and reproduction. In addition, when the Ag-based alloy of the present invention is used for a film for electromagnetic wave shielding, aggregation of Ag is less likely to occur, and it is less likely to cause a decrease in electromagnetic wave/mask characteristics or white spots due to disappearance of conductivity due to aggregation of Ag. Therefore, it can improve the durability. The sputtering target for forming a Ag-based alloy film of the present invention is suitably used for film formation of such a film for electromagnetic wave shielding. In addition, when the Ag-based alloy of the present invention is used for a light-reflecting film of a liquid crystal display device, it is possible to provide a high-performance light-reflecting film having a high light reflectance which is almost equal to the original high light reflectance of Ag, and A liquid crystal display element of a light reflecting film. The sputtering target for forming an Ag-based alloy film of the present invention is suitably used as a film of a light-reflecting film of such a liquid crystal display element. -15- (12) 1265976 DETAILED DESCRIPTION OF THE PREFERRED SYSTEM First, a preferred system of the first invention will be described. The present inventors have focused on the above-mentioned problems to provide an Ag-based alloy reflective film or a semi-transmissive reflective film for an optical information recording medium having thermal conductivity, high reflectance, and high durability. As a result, it was found that the Ag-based alloy containing and/or having a total Sb of 0.005 to 0.40% has not only high reflectance and high thermal conductivity which can be correlated with pure Ag, but also can exceed the high level of durability of pure Ag. The present invention has been completed. The invention is described in detail below. The Ag-based alloy reflective film or the transmission-reflecting film for an optical information recording medium of the present invention is composed of an Ag-based alloy containing 0.005 to 0.40% of Bi and/or Sb as a necessary element. The reflective film or semi-transmissive reflective film made of such an Ag-based alloy has not only high thermal conductivity and high reflectance comparable to pure Ag, but also excellent durability (thermal stability and chemical stability). ® In general, a pure Ag film formed by sputtering or the like contains a plurality of crystal defects (holes, translocation 'grain boundaries, etc.), and Ag is easily dispersed by the crystal defects, so if it is placed in a high-temperature and high-humidity environment, it is pure. In the Ag film, atoms diffuse and aggregate in various places to increase the surface roughness or crystal grain size. In addition, Ag atoms are also diffused and aggregated in an environment containing a halogen ion such as a chloride ion. The change in the surface of the film resulting from such agglomeration causes a decrease in the inversion rate, which significantly deteriorates the characteristics of recording and reproduction of the optical disk. In particular, in the extremely thin semi-transmissive reflective film of the DVD-ROM, the influence of the aggregation due to agglomeration is large, and the characteristics of recording and reproduction of the optical disk are remarkably deteriorated. Gao Bi has a half-construction of the lack of expansion Ag is also easy to shoot in the anti-16- (13) 1265976 as a solution to the above problem 'has been discussing the alloying of Ag, proposed to add precious metal elements in Ag ( Au, Pd, Pt, etc.), or alloying of rare earth metal elements (Y, etc.). However, when alloying is performed by adding a noble metal element (Au, Pd, Pt, etc.) to Ag, it is possible to suppress aggregation of Ag atoms affected by chloride ions or the like, but it is not possible to suppress Ag atoms placed under high temperature and high humidity. Agglutination. In addition, the addition of a rare earth metal element (Y or the like) to the alloying method suppresses aggregation of Ag atoms placed under high temperature and high humidity, but does not inhibit aggregation of Ag atoms affected by chloride ions or the like. That is, the alloying of * with any element group cannot simultaneously suppress the aggregation of Ag atoms from both sides affected by the high temperature and high humidity. - According to the present invention, by forming an Ag-based alloy having a total content of Bi and/or Sb of more than 0.005%, it is possible to simultaneously suppress aggregation of Ag atoms which are affected by high temperature and high humidity and chlorine ions. Further, these elements were confirmed to exhibit a more specific agglutination inhibitory effect as their content increased. However, the addition of the above elements to Ag has a tendency to lower the thermal conductivity and the reflectance of the pure Ag film, which is remarkable as the content of the above elements is increased, and as a result, the thermal conductivity and reflectance of the Ag underlying alloy film are lowered. For the content of the above elements, the upper limit of the total content can be increased to 3% from the viewpoint of ensuring high reflectance for the blue-violet laser for the next-generation optical disc. However, if the total content exceeds 〇·40%, the high thermal conductivity required for the reflective film of the high-speed DVD or the next-generation optical disc cannot be ensured. Therefore, as an element for ensuring both high reflectance and high thermal conductivity, The upper limit of the weight is defined as 0.40%. On the other hand, if the total content is less than -17-(14) 1265976 Ο · Ο Ο 5 %, the effect of adding B i and/or s b can not be effectively exerted. Suitably 〇 · Ο 1% or more, 〇 · 3 % or less, more: 〇 . 〇 5 % or more, 〇 · 2 % or less. In view of the production of a sputtering target, etc., Bi is suitably used in terms of excellent workability. In the present invention, in order to further improve the durability, particularly the thermal stability, of the alloy containing Bi and/or Sb, it is effective in addition to the above-mentioned element rare earth metal element. These elements have a Nd and/or Y which is suitable for suppressing agglomeration of Ag atoms caused by high-level placement and further improving durability. For the above, the content of these elements of the metal alloy is suitably Nd and/or Y total • Above, 2% or less. If it is less than 0.1%, the effect of adding by the element cannot be obtained, and if the content exceeds 2%, the high number cannot be obtained. More preferably, the upper limit is 1%, and more preferably 0.5%. Further, in order to improve the durability of the Ag substrate containing Bi and/or Sb, especially chemical stability, at least one selected from the group consisting of B Au, Rh, Pd may be added. Or the element of Pt. These elements have an effect of suppressing the aggregation of Ag atoms which are further affected by the influence of the particles, and further improve the durability. The aggregation suppressing effect of these Ag atoms is effectively exhibited, and is preferably 0.1% or more and 3% or less in total. A more suitable upper limit is 2%. Further, in order to further improve the chemical stability of the Ag-based alloy, it is also effective to add Mg, Ti, and Zn to the above elements. The durability improvement effect of adding these elements is inferior to that of Au, Rh, Pd, and the cost of raw materials, which is advantageous in reducing the cost of the optical disc. If the content of Ti and Zn is large, the thermal conductivity and the reflectance are lowered. The agglutination is suitable, and the effect of temperature and high humidity is contained from the outside of the operation. Ag bottom 0.1% Cu of the above-mentioned elemental thermally conductive bismuth alloy is affected by chlorine. In order to characterize S, although Pt is added, but Mg, this -18 - (15) 1265976 is limited to the total Q weight of these alizarins. 3 %. Of course, a sufficient effect can be obtained by adding one of the above alloy element groups, but the same effect can be obtained by combining two or more types. However, the above effect obtained by adding Nd and/or Y as a rare earth metal element or the addition of at least one element selected from Cu ' Au, Rh, Pd or Pt is an Ag bottom containing Bi and/or Sb. The unique effects that the alloy can achieve, such as the same effect in pure A g. It is also disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Nb, Fe, Ta, Hf, Ga, Pd, Bi, In,

At least one element of W or Zr enhances the _ corrosive Ag alloy. However, Al, An, Cu, Pt, and Pd do not have an effect of suppressing aggregation of Ag atoms generated when an Ag thin film is placed at a high temperature, and durability improvement cannot be obtained from the viewpoint of thermal stability as a problem to be solved in the present invention. effect. Further, addition of 0.5% or more of Bi lowers the thermal conductivity, so that it is not good and is removed from the present invention. Further, Japanese Laid-Open Patent Publication No. 2002-92959 discloses the improvement of chemical stability by adding 4 to 15% by mass of Cu and 0.5% by weight of Al, Zn, Cd, Sn, Sb and Ir to Ag. Balance. However, Cu, Al, Zn, Cd, Sn, and Ir cannot obtain an aggregation suppressing effect according to Ag atoms placed at a high temperature. In addition, if the addition of Sb exceeds 0.5% by weight (0.44%), the original thermal conductivity of Ag is lowered, so it is not good. Therefore, these known Ag alloys are clearly distinguished from the present invention in view of their specific constitution and effects. The Ag-based alloy reflective film for an optical information recording medium of the present invention or the Ag-19-1265976 (16) semi-transmissive semi-transmissive reflective film can be formed on a substrate by a true-vapor deposition method, an ion plating method, or a sputtering method. It is obtained by filming an Ag-based alloy composed of the alloy, and it is recommended to form a film according to a sputtering method. The Ag-based* alloy reflective film and the Ag-based semi-transmissive reflective film formed by the sputtering method are superior in film in-plane uniformity of alloy element distribution or film thickness as compared with a film formed by another film forming method. It can exhibit high level of characteristics (high thermal conductivity, high reflectivity, and high durability) as a reflective film, and can produce a high-performance and highly reliable optical disc. Further, the Ag-based base material anti-reflection film for an optical information recording medium of the present invention is used as a reflection film for single-layer recording which is recorded only on one side of the optical disk, or as the uppermost reflection film for multi-layer recording. The film has a transmittance of 0%, and the reflectance is determined by the disk composition, but is approximately 45% or more. Further, the film thickness can be appropriately selected within a range satisfying the above reflectance and transmittance, and can be, for example, about 50 to 200 nm. Further, the semi-transmissive reflective film of the present invention is a film which is used as a reflection film of a medium for performing multi-layer recording on a single side of a disk, and the transmittance and reflectance are determined according to the disk configuration, but generally have 60 to 72. A film with a degree of transmittance and a reflectance of 18 to 30%. Further, the film thickness can be appropriately selected within a range satisfying the above-mentioned reflectance and transmittance, and the standard can be about 5 to 20 nm. The Ag-based alloy sputtering target for an optical information recording medium of the present invention can be produced by any method such as a dissolution casting method, a powder sintering method, or a spray method. Among them, it is particularly preferable to manufacture it according to a vacuum dissolution casting method. The Ag-based alloy sputtering target produced by the vacuum dissolution casting method has a smaller content of impurities such as nitrogen-20-(17) 1265976 or oxygen than the other methods, and a reflective film or a half formed by using the sputtering target. The high-performance (high thermal conductivity, high reflectance, and high durability) of the reflective film can be satisfactorily exhibited by the reflective film, and a high-performance and reliable optical disc can be produced. The reflective film or the semi-transmissive reflective film of the present invention must contain 0.005 to 0.40% of .Bi and/or Sb as above, but in order to obtain a film having a composition in which the content of Bi is particularly high, the sputtering crucible needs to contain germanium. 〇4~ Φ 4.5% Bi. In a general alloy system, such as an Ag-Cu alloy system, an Ag-precious metal alloy, or a film such as an Ag-rare earth metal alloy, the composition of the sputtering target and the composition of the film are almost the same. In this case, when a film is formed using a Ag-based gold alloy sputtering target containing Bi, the amount of Bi in the film is reduced by several to several tens of % of the amount of Bi in the sputum. This may be because, l) the difference between the melting points of Ag and Bi is large, or the vapor pressure of B i is higher than that of A g , so b丨 re-evaporates from the substrate side during film formation, or 2) Ag Since the sputtering rate is larger than the county rate of B i , B i is not easily sputtered. Further, 3) B i is easily oxidized than A g , so only Bi is oxidized on the surface of the oscillating target without being sputtered or the like. The reason is that the amount of Bi in the film is smaller than the amount of Bi in the sputtering target. Therefore, it is necessary that the content of Bi in the sputtering target of the present invention is more than the content of Bi in the reflective film and the semi-transmissive reflective film, for example, in order to obtain a reflective film and a semi-transmissive reflective film containing 0.005 to 0.40% of Bi. It is necessary to consider the content of Bi which does not enter the film, and the content of Bi in the sputtering target is 0.05 or more and 4.5% or less, suitably 0.1 or more and 3.6% or less. -21 - (18) 1265976 The above phenomenon is not observed in other Ag alloy systems such as Ag-Sb alloy system and Ag-based system. The composition of these 'sputter targets and films formed using the film is almost the same. For other elements other than Bi, a sputtering target containing various elements in a range can be specified. The optical information recording medium of the present invention is preferably provided with an alloy reflective film or a semi-transmissive reflective film. The other light/structure is not particularly limited, and all of the components can be recorded by optical information. However, the transparent substrate such as polycarbonate has a single-Ag substrate. Reflective film or semi-transmissive reflection of alloys. Information recording medium with light reflectivity and high thermal conductivity - not only suitable for read-only type, write-once type, I-recorded medium' speed is suitable for single-speed DVD or Next - Next, the present invention is carried out as follows for the preferred system of the second invention. ® Preparation of an Ag alloy film for a spatter magnetic wave mask comprising at least one of Bi: 0.2 to 23 at%, Sb: (hereinafter also referred to as atomic %), and an Ag alloy satisfying the following formula (2 - 1 ) In the sputtering method, the Ag target film of the electromagnetic wave mask of the present invention containing 0.01 to 10 atoms in total of the film Bi and/or Sb such as transparent glass is used in combination with the sputtering target. The body is formed of an Ag alloy film by a magnetic wave mask. 〇·〇1 Atomic %S 0.000502X3 + 0.00987X: The rare earth metal alloy is consistent in the Ag base alloy. Accordingly, the present invention is known in the art of a medium which satisfies the above-described Ag-based information recording medium of the present invention. The optical information of the present invention having the above-mentioned film and the high-endurance, rewriting type and the like are included. Description. 〇.〇1 to 10 atom% of the amount of Bi and Sb amount of the target (the gold sputtering target of the present invention). The constituting substrate is formed into an Ag alloy film of 6 (this gives the present invention an electric + 0.0 5 5 3 X + Sb amount -22-(19) 1265976 $10 atom% ...... Formula (2-1) In the formula (2 - 1), X is the amount of Bi (atomic %) in the sputtering target (Ag alloy), and the amount of Sb is Sb • (atomic %) in the sputtering target (Ag alloy). In order to attain the object of the present invention, the inventors of the present invention use an Ag-based alloy sputtering target produced by adding various elements to Ag to form an Ag alloy composed of various components by a sputtering method. The film and the valence were used as the characteristics of the Ag alloy film for electromagnetic wave shielding. As a result, it was found that • in the case of an Ag alloy film having Bi and/or Sb, migration of Ag can be suppressed> 凝 aggregation is less likely to occur, and the present invention has been completed. DETAILED DESCRIPTION OF THE INVENTION The Ag-base alloy consisting of an Ag-based alloy containing one or more elements of Sc, Y and a rare element was invented by the present inventors (Sakamoto Tetsui 13-351572/2001) No.) with pure Ag or containing Pd, Pt, Sn, Zn, In, Cr, Ti, Si, Zr, Nb and ® An Ag-based alloy phase composed of an Ag-based alloy of one or more elements has excellent Ag-resistant agglomeration, and thus exhibits durability (the Ag alloy film does not deteriorate for a long period of time) and weather resistance (for high-temperature, high-humidity rings) In view of the above, it is found that the Ag alloy film (the electromagnetic wave shielding A g alloy film composed of an Ag alloy containing 0.01 to 10 atom% of Bi and / or Sb in total) is A. The aggregation suppressing effect of g is more excellent, and a sufficient effect can be obtained with a slight addition, and at the same time, the electric resistance can be further reduced. Further, the amount of the material containing one of Sc, Y, and a rare earth element is added to the soil film. Ta is an Ag-based alloy film composed of an Ag-based alloy of -23-(20) 1265976 on the surface/cover (Japanese Patent No. 1 3 - 3 5 1 5 72 / 200 No. 1), although Although it is excellent in durability against oxygen or moisture in the atmosphere, sufficient durability cannot be obtained in an atmosphere containing a halogen element such as brine, and the Ag alloy film according to the present invention exhibits sufficient durability against salt water. Invented Ag alloy film By appropriately controlling the addition amount of the additive element (Bi and/or Sb ), an Ag alloy film capable of exhibiting characteristics corresponding to electromagnetic wave length (that is, infrared masking property and radio wave shielding property) can be obtained. In the case of the infrared mask, it means that the wavelength (one person) is 8 X 1 (the shielding property of a long wave of T 7 m or more. In addition, the case of using the electric wave shielding cover means that the wavelength (λ) is 1 (The coverage of long waves of T 3m or more. For the addition amount (content) of these additional elements (Bi and/or Sb), the total amount thereof is required to be 〇1〇1〇1 atom%. When a total of 0.01 atom% or more of Bi and/or Sb is added, it is possible to effectively suppress the growth of crystal grains due to surface diffusion of Ag. In particular, an Ag alloy film containing 0.05 atom% or more in total of Bi and/or Sb is superior in chemical stability (especially weather resistance) to a pure Ag film, and therefore, aggregation inhibition effect of an Ag alloy film even when exposed to a high temperature and high humidity environment It is also high, and the electromagnetic wave shielding property is also extremely excellent. • In particular, where the substrate is a compound containing oxygen, B i and/or

Since Sb has high affinity with oxygen, it diffuses and concentrates on the substrate interface to improve adhesion. Thereby, the agglutination of A g is further reduced. Further, if the surface of the Ag alloy film is exposed to an oxygen atmosphere, Bi and/or Sb -24· 1265976 (21) in the Ag alloy film diffuse and concentrate on the surface of the Ag alloy film to form an oxide layer (Bi and / or. Sb oxide layer). Since the oxide layer is blocked from contact with the environment, the aggregation suppressing effect of Ag is further enhanced. 1 to 2 show the results of the composition analysis of the thickness of the XPS (X-ray photoelectron spectroscopy) of the Ag-Bi alloy film having a thickness of about 20 nm formed on a glass substrate (Fig. 1) and the narrow-field spectrum of Bi (Fig. 1) Figure 2) shows that Bi is concentrated on the outermost surface, and from the narrow-area spectrum of Bi, the most surface-concentrated B i forms an oxide. On the other hand, the inside of the Ag-Bi alloy film was sputtered from the surface of the film for 1 minute, 2 minutes, 3 minutes, and 4 minutes, and the peak of the Bi of the XPS was obtained. It can be known that only the outermost surface is oxidized. In addition, the thickness of the oxide layer was analyzed by RB S (Rutherford Backscattering). The result was the thickness of several atomic layers. Further, the composition of B i on the interface between the glass substrate and the Ag alloy film was also higher than that inside the A g alloy film, and thus it was confirmed that the composition was concentrated. As described above, the oxygen and chemical layers of Bi and/or Sb are densely formed, and in view of the contact with the environment, it is preferable that Bi and/or Sb are contained in an amount of 0.05% by atom or more in total. That is, the lower limit 添加 of the addition amount of the more preferable additive element (Bi and/or Sb) is 〇·〇5 atom%. Λ Regarding the upper limit of the addition amount of these additive elements (Bi and/or Sb), even if the addition amount is increased, the element addition effect is saturated' and the low visible light transmittance is lowered, so it is set to .1 〇 atom%. When the Ag alloy film is used, it is preferably 5 atom% or less, more preferably 3 atom% or less, and further preferably 1 atom% or less. When used as an A g alloy film for a radio wave mask, if the amount of addition is large, the resistance of the Ag alloy film will increase, and the -25-(22) 1265976 method will obtain sufficient radio wave masking property, so the upper limit of the _ recommended is 55. The atomic %, more preferably, the upper limit 値 is 3 atom%, and a suitable upper limit 値 is 1 atom%. In particular, in order to exhibit excellent radio wave masking properties for a long wave having a wavelength of 1 〇 _ 1 m or more, the upper limit 値 is suitably 5 atom% to reduce the electric resistance, and more preferably, the upper limit 値 is 3 atom%, and further suitably The upper limit is 1 atom%. The addition amount (content) referred to herein is a composition of Bi and/or Sb for the entire Ag alloy film containing a concentrated layer of Bi and/or Sb. The Ag alloy film for an electromagnetic wave mask of the present invention contains, as described above, a total of 0.01 to 10 atom% or more of Bi and/or Sb. At this time, if at least one element selected from the group consisting of Cu, Au, Pd, Rh, Ru, .Ir, or Pt is contained in an amount of 0.3 atom%, the chemical stability of Ag is further increased and suppressed. The effect of Ag agglutination will increase. In particular, these elements (Cu, An, Pd, Rh, Ru, Ir, and Pt) do not decrease the reflectance or the electric resistance as the amount of addition increases, so that the additive resistance of Ag can be improved by the addition of '. The amount of addition of these elements (Cu, Au, Pd, Rh, Ru, Ir, and Pt) is more preferably 55 atom% (atomic %) or more and more preferably 0.8 atom% or more. On the other hand, the upper limit of the amount of addition is not particularly limited, and if it exceeds 10 atom%, the visible light transmittance decreases as the element addition effect is saturated, and the electric resistance is increased, so that sufficient radio wave masking property cannot be obtained, so these elements (Cu The upper limit of the amount of addition of Au, Pd, Rh, Ru, Ir, and Pt) is suitably 10 atom%, more preferably 8 atom% or less, and most preferably 5 atom% or less. Further, when a rare earth element such as Sc, Y or Nd is added to the Ag alloy film of the present invention, the aggregability of -26-(23) 1265976 A g can be further suppressed. These addition amounts are suitably 〇 1 atom% or more, preferably 0.2 atom% or more. On the other hand, from the viewpoint of electrical resistance, it is suitably 1 atom%, more preferably 0. 8 atom% or less, and most preferably 6 atom% or less. Further, depending on the application, other components than the above components may be added to the extent that the effects of the present invention are not impaired. Such a component may be added such as Ta, Co, Zn, Mg, Ti or the like. It does not matter if Φ contained in the raw material beforehand is introduced into the film. The thickness of the Ag alloy film for the electromagnetic wave mask of the present invention is not particularly limited, and may be changed according to requirements such as electromagnetic wave mask characteristics or visible light transmittance. Suitably 3 nm or more and 20 nm or less. If not, sometimes sufficient electromagnetic wave mask characteristics are not obtained. From the relevant side, it is more preferably 5 nm or more, and most preferably 8 nm or more. When used for a cover, the film thickness is suitably 5 nm or more, more preferably 8 nm or more preferably 10 nm or more. Further, from the viewpoint of obtaining sufficient visible light transmittance, it is preferably 20 nm or less, more preferably 18 nm or less and preferably 1 5 n or less. In the present invention, in order to reduce the glare caused by visible radiation according to the Ag alloy film, other films may be formed outside the Ag alloy film, and a substrate may be provided between the substrate and the Ag alloy film for electromagnetic wave shielding. The bottom layer is not particularly limited, but is suitably transparent from the viewpoint of visible light transmission. Further, in order to improve the adhesion of the Ag alloy body, a primer layer may be provided. Further, the bottom layer is suitably sizable, so that the heat ray mask effect and the electromagnetic wave mask effect can be improved, and the upper limit is suitable, and the impurity is also positively added. The characteristic is suitable for the 3 nm surface to observe the electric wave. The angle of the pass, the best of the light. For example, layer. Shape Angle The film and the base are electrically conductive. Fruit, -27- (24) 1265976 Appropriately select the bottom layer of the composition having the desired purpose characteristics. Examples of such a primer layer include an oxide film whose main components are oxides of zinc oxide, tin oxide, titanium oxide, indium oxide, ITO, cerium oxide, zirconium oxide, or aluminum oxide, or whose main components are tantalum nitride, aluminum nitride, and nitrogen. A nitride film of a nitride such as boron, and an oxynitride film of an oxynitride such as a sialon heat-resistant ceramic. As a matter of course, the single oxide or two or more mixed oxides or a mixture other than the oxide may be used as the underlayer (base film), and the composition of the underlayer is not particularly limited, but Bi and/or Sb are easily bonded to oxygen. Therefore, if the underlayer film contains oxygen, the interface between the underlayer film and the Ag alloy film is likely to diffuse Bi and/or Sb and concentrate, so that the adhesion is improved. Therefore, from the viewpoint of improving the adhesion, a film containing oxygen such as an oxide or an oxynitride is suitably used in the under film. These underlayers may be a single layer or a stratified layer, and the base film of the above-described examples and the film of the composition outside the underlayer may be combined as a composite layer. Among them, a high refractive index such as titanium oxide is suitably used as the underlayer because it is possible to suppress light reflection and to obtain sufficient visible light transmittance. The method for forming the underlayer (underlayer) is not particularly limited, and may be formed on a substrate by a method suitable for the composition of the underlayer film, and examples of the method include a sputtering method, a plasma CVD method, a sol-gel method, and the like. The film thickness of the under film is not particularly limited, but it is usually recommended to be about 10 nm to 1 OOO nm. If it is thinner than 1 〇 nm, the desired purpose cannot be obtained. For example, it is impossible to reduce the light reflectance while ensuring sufficient visible light transmittance. In addition, if it is larger than 1 〇 〇 〇 nm, there is a possibility that the adhesion of the film stress is lowered, so it is not good. More suitably, it is below l〇〇nm. -28- 1265976 (25) In order to improve the durability and weather resistance for the same purpose as the bottom layer, or to improve the chemical resistance, abrasion resistance, scratch resistance, and Ag aggregation resistance of the use environment, A protective film is provided on the Ag alloy film. The protective layer formed on the Ag alloy film for electromagnetic wave shielding is not particularly limited, but is preferably transparent from the viewpoint of visible light transmittance, and is preferably an amorphous film from the viewpoint of durability against oxygen or moisture. . • A film having the same composition as that of the above-mentioned base film can be used as the protective film, and a film exemplified as the above-mentioned primer layer is suitably used as the protective layer. Among them, from the viewpoint of abrasion resistance and scratch resistance, a protective layer is suitably selected from alumina, tantalum nitride, aluminum nitride, boron nitride, yttrium aluminum oxynitride polymer, and the like. Further, in view of weather resistance and durability against an atmosphere containing a halogen element such as salt water, an oxide or oxynitride is suitably used. This is because when the protective film is an oxide film containing oxygen or an oxynitride film, oxygen is formed during the film formation process, so Bi and/or Sb diffuse onto the Ag alloy film and oxidize to form an oxide, and the root is based on Bi and / Or the oxide layer of Sb improves the barrier property to the environment, improves the adhesion to the protective film, and reduces the pores of the protective film, thereby further improving the environmental barrier property. In particular, from the viewpoint of the adhesion to the concentrated layer of Bi and/or Sb or the small number of pores, ITO or zinc oxide, tin oxide or indium oxide is suitably used in the oxide. These protective layers can be single layers or 'multilayers'. Further, in the case of the stratification, a film of the above-exemplified protective layer and a composition outside the protective layer may be combined as a composite layer. The method for forming the protective layer is not particularly limited, and may be formed on the Ag alloy film by a method suitable for the composition of the protective layer. Examples of the method include sputtering -29-1265976 (26), plasma CVD, and sol-gel method. Wait. The film thickness of the protective film is not particularly limited, but it is generally recommended to be about 10,000 nm. If it is thinner than 10 n m, sufficientness and scratch resistance are not obtained, and the pores cannot be sufficiently reduced. Further, at 100 nm, there is a possibility that the adhesion of the film stress is lowered, so that it is preferably 100 nm or less. Alternatively, the underlayer and the Ag_protective layer may be alternately laminated on the substrate. The present invention forms a base of an Ag alloy film (or a bottom layer thereof), a glass, a plastic, a resin film, etc., but is used for window glass, etc., and is preferably used in a substrate having transparency (see:). . In this case, the material thickness and the like are not particularly limited as long as the visible light is transmitted. In addition, the substrate is not required to have transparency. When an Ag alloy film is used for the purpose of radio waves, such as an internal electronic device or an external Ag alloy film, the type, composition, thickness, and material of the substrate are not particularly limited. In the present invention, the substrate may be used singly or in a plurality of layers, and in order to further improve the characteristics, various bodies and/or at least one layer of the Ag alloy film for electromagnetic wave shielding, a combination underlayer, and a protective layer may be used as the composite layer. That is, the electromagnetic Ag alloy film forming body of the present invention can form the electromagnetic Ag alloy film of the present invention on a substrate. Further, a film containing at least one of a nitride, a nitride, and an oxynitride may be formed on the substrate as an underlying layer to form an Ag alloy film for an electromagnetic wave mask of the present invention, and the wear resistance of the > 1 Onm 〜 More than bad. The alloy film and the body are exemplified by a light-transmitting property and a composition, that is, a mask is mainly formed, and a combination of a transparent base is used, and the self-oxide is used for the wave mask for the wave mask. The bottom Ag substrate -30-1265976 (27) forms at least one film selected from the group consisting of oxides, nitrides, and oxynitrides as a protective layer on the alloy film. For example, when it is used for applications requiring visible light transmission, it is recommended to form an 'Ag alloy film or the like on the indoor side. If it is formed on the outdoor side, it is not good because there is a large possibility of scratches on the external factor (small stone or dust, etc.). In addition, even if it is installed on the indoor side, there is a possibility that a flaw is generated on the film according to the external factor. It is generally suitable to use a film in which an Ag alloy film or the like is not directly exposed to an outdoor environment. Thus, the Ag alloy film forming body of the present invention may be a single layer of a substrate, but is protected from an external factor* by an Ag alloy film. In view of the above, a combination of a plurality of substrates may be used. The combination in the case of forming a composite layer is not particularly limited. For example, when a glass having transparency is used as a substrate, a so-called laminated glass or interlayer may be exemplified. Glass. Considering the indoor heat insulation and sound insulation required for the living environment. From the viewpoint of durability, the recommended substrate is laminated glass or laminated glass. The combination of the laminated glass is not particularly limited. Suitably seal the mask into ' ^ if multiple sheets of glass are used, separate partitions between adjacent glass sheets, etc., to kill, air layer (space layer). From the viewpoint of corrosion between the glass plates, it is preferable to enclose dry air or nitrogen gas in the space layer. Further, the .A g alloy film is suitably formed on the side of the air layer of the outer glass or the side of the air layer of the inner glass, thereby preventing It is injured at the time of production at the factory. In addition to the case where a transparent glass is used as the substrate, the same applies to the case of using a transparent body. It is recommended to form an Ag alloy film on a substrate (transparent substrate) made of a transparent body (or further A layered structure of a transparent body is laminated on the protective layer formed on the Ag alloy film, at which time a transparent body is suitably laminated via a separator, and the film is laminated under the transparent body and the film thereunder A space layer is provided between the (Ag alloy film or the protective layer). When the Ag alloy film of the electromagnetic wave mask of the present invention is used for applications that do not require visible light transmission, it can be used in a machine type cover such as an electronic device that requires a radio wave mask. An Ag alloy film is formed on the inner side and/or the outer side, or an Ag alloy film is formed on any surface of the radio wave mask sheet. Of course, in order to protect the Ag alloy film from external factors as described above It can be made into a multi-layer or a base layer or a protective layer depending on the application. Of course, it is also possible to attach a laminated film of an Ag film such as a polymer film to a substrate, or to have an Ag/film inside or outside the machine. The Ag alloy film for an electromagnetic wave mask of the present invention is preferably formed on the substrate by a sputtering method. When the pure Ag film is formed on the substrate by a sputtering process or the like, the film thickness becomes an island when the film thickness is several tens of nm. The film is in a state of surface energy of Ag, and if the Ag film is in direct contact with air, the surface energy of Ag is further increased. Therefore, in order to lower the surface energy, aggregation of Ag is likely to occur. However, 'add Bi and/or Sb. Since the Ag alloy film has a low surface energy, the surface diffusion of Ag is suppressed, and aggregation can be suppressed. In particular, if exposed to an aerobic atmosphere, an Ag alloy film to which Bi and/or Sb is added is diffused on the Ag surface. / or Sb combines with oxygen to form an oxide, which blocks the Ag alloy film and the environment while reducing the surface energy of Ag, thereby suppressing the surface diffusion of Ag and suppressing aggregation. It is considered that by adding one or more elements of Cu, Au, Pd, Rh, Ru, Ir, or Pt to the Ag alloy film, the surface energy is further lowered, thereby suppressing aggregation of Ag. In addition, the additive element Bi and/or Sb according to the present invention is such that if oxygen is contained in the substrate or the base film and the protective film of 32-(29) 1265976, Bi and/or Sb diffuse and concentrate on the surface of the Ag alloy film. The composition of Bi and/or Sb inside the Ag alloy film is reduced. As a result, the resistivity is lowered and the radio wave mask characteristics are extremely excellent. The sputtering target for forming a film by the sputtering method for the electromagnetic wave mask may be at least one selected from the group consisting of Bi: 0.2 to 23 at% and Sb: 0.01 to 10.0 at%, and the amount of Bi and the amount of Sb. A sputtering target composed of an Ag alloy of the formula (2 - 1) is satisfied. At this time, the sputtering target material is suitably used in an Ag-based alloy (hereinafter also referred to as a dissolved Ag-based alloy target material) produced by a dissolution casting method. The dissolved Ag substrate target material involved in the material is uniform in structure, and the sputtering rate and the exit angle are uniform, so that a stable Ag composition and a gold film can be obtained stably, and the result can be obtained. A higher performance Ag alloy film former. If the oxygen content (suitably 100 ppm or less) of the above-mentioned molten Ag-based alloy target material is controlled, it is easy to maintain a certain film formation speed, and the oxygen content in the Ag-based alloy film can be lowered, so that the Ag alloy can be improved. The corrosion resistance of the film. In this case, a sputtering target composed of an Ag alloy containing at least one of Bi: 0.2 to 23 at%, Sb: 0.01 to 10 at%, and a Bi amount and an Sb amount satisfying the formula (2 -1 ) can be used. A sputtering target (hereinafter also referred to as a target) for obtaining an Ag alloy film for electromagnetic wave mask containing 0.01 to 1 atom% of Bi and/or Sb in total. When an Ag alloy film is formed by a sputtering method using a Bi-containing Ag-based alloy*, the amount of Bi in the Ag alloy film is less than the amount of Bi in the target, and quantitatively is a few % of the amount of Bi in the target. Dozens of percent. Therefore, as a target for obtaining a Bi-containing Ag alloy film, it is necessary to use a target containing more Bi than the amount of Bi in which the Ag alloy film is to be obtained, specifically -33-(30) 1265976, as a material for obtaining Bi. : A target of an Ag alloy film of 0.01 to 1 〇·〇 atom% is required to use a target containing Bi: 0.2 to 23 at%. The target involved in the present invention is a target having the above composition. In other words, when Bi is contained, it is required to be a target having a composition of Bi more than Bi to obtain an Ag alloy film, and a target composed of a Bi-containing Fe-based alloy is used by sputtering. When the Ag alloy film is formed, the amount of Bi in the Ag alloy film is smaller than the amount of Bi # in the target. The reason is that Bi has a lower melting point than Ag, and the difference between the melting points of Ag and Bi is large, so Bi is re-evaporated from the substrate side during film formation (during sputtering), and/or, the sputtering rate of Ag is larger than Bi. Since the sputtering rate is such that Bi is not easily sputtered, and/or B i is easily oxidized than Ag, the surface of the sputtering target - only Bi is oxidized without being sputtered or the like. As described above, the total amount of Bi and Sb contained in the Ag alloy film needs to be 原子·〇1 atom% or more and 10 atom% or less. Therefore, the amount of Bi and Sb contained in the target needs to satisfy the formula (2 - 1). This is also because the amount of Bi ® contained in the target is different from the amount of Bi contained in the Ag alloy film. The coefficient of the amount of Bi in the target in the formula (2 - 1) (g port, 0·0005 02Χ3 + 0.0 09 8 7Χ2 + 0·05 5 3 Χ This formula and its coefficient) is the amount of Bi in the experimental target After the correlation with the amount of Bi in the Ag alloy film, the results are approximated. When the Ag alloy film for an electromagnetic wave mask according to the present invention is used for a radio wave mask, at least one of Bi: 0.2 to 12 at% and Sb: 0.01 to 5 at% is used, and the amount of Bi is A sputtering target composed of an Ag-based alloy having the Sb amount satisfying the following formula (2-2). -34- (31) 1265976 〇·〇! Atomic %S0.000502X3+0.00987X2+0.0553X+Sb Amount '5 Atomic % ...... Formula (2 - 2) In the above formula (2-2), X is the amount of Bi (atomic %) in the target, and the amount of Sb is the amount of sb (atomic %) in the target. The conditions of the sputtering method are not particularly limited, and a known sputtering method can be used. When it is used as a sputtering target for an infrared mask, it is preferable that the main component is Ag' and contains at least one of Bi: 2 to 12 atom% and Sb: 0.05 to 5 atom%, and the amount of Bi and the amount of Sb satisfy. Further, at least one of Bi: 〇·5 to 8 at% and Sb: 0.10 to 3 at% may be contained in the above formula (2-3), and the amount of Bi and the amount of Sb satisfy the following formula (2-4). 〇·〇5 Atomic %s〇.〇〇〇5〇2X3 + 0.00987X2 + 〇.05 5 3 X + Sb 纛S 5 atom% ...... Formula (2 — 3 ) 〇·1〇 atomic % $ 0.000502X3 + 0.00987X2 + 0.0553X + Sb 纛 '3 atom% ...... Formula (2 - 4) In the above formulas (2~3), (2-4), X is the amount of Bi in the target (Atomic %) and the amount of Sb is the amount of Sb (atomic %) in the target. When it is used as a sputtering target for a radio wave mask, it is preferable that the main component is Ag and contains at least one of Bi: 2 to 12 at% and Sb: 0.01 to 5 at%, and the amount of Bi and the amount of Sb satisfy. In the above formula (2-5), it is more preferable to contain at least one of Bi: 〇·5 to 8 at% and Sb: 0.5 to 3 at%, and the amount of Bi and the amount of Sb satisfy the following formula (2-6). Further, at least one of Bi: 〇·5 to 5 at% and Sb: 0·10 to 1 at% may be used to satisfy the following formula (2-7). 0.01 Atomic % S 0.0005 02X3 + 0.009 8 7X2 + 0.05 5 3X + Sb Amount -35 - 1265976 (32) Atomic % ...... Formula (2-5) 0.05 Atomic% $ 0.0005 02乂3 + 0.0098 7) (2 + 0.05 5 3 > ( + 313 S3 atomic % ...... Formula (2-6) ' 0· 1 0 Atomic % S 0.0005 02X3 + 0.009 87x2 + 0.05 5 3X + Sb Atomic % .. .... Formula (2-7) In the above formulas (2-5), (2-6), and (2-7), 'X is the amount of Bi in the target (atomic %), and the amount of Sb is sb in the target. Amount (atomic %) ° # If these targets contain at least one element selected from the group consisting of at least one of Cu, Au, Pd, Rh, Ru or Pt, it is possible to further improve the aggregation inhibition effect of Ag. The addition amount of these elements (Cu, Au, Pd, Rh, -Ru, Ir, and Pt) is more preferably 〇5 atom% or more, and suitably 0.8 atom% or more. On the other hand, these elements (Cu, Au) The upper limit of the amount of addition of Pd, Rh, Ru, Ir, and Pt) is not particularly limited, but the upper limit is suitably 10 atom%, more preferably 8 atom%, and most preferably 5 atom%. Add the above added elements (Bi and /or

Sputter target of Sb, or further selected from one or more of Cu, Au, Pd, Rh, Ru, Ir, or Pt, in accordance with a sputtering method, an electromagnetic wave mask for an Ag alloy film in addition to electromagnetic wave mask characteristics (ultraviolet mask) Excellent in terms of properties and radio wave shielding properties, and excellent in visible light transmittance, durability, weather resistance, and Ag aggregation resistance. The Ag alloy film for an electromagnetic wave mask according to the present invention is preferably formed by a sputtering method as described above, but may be formed by a chemical vapor deposition method such as a vacuum deposition method or a chemical vapor deposition method such as a CVD method. -36- 1265976 (33) In the present invention, as described above, the surface and/or interface of the Ag alloy film has a layer having a larger content of Bi and/or Sb than the inside of the Ag alloy film (hereinafter also referred to as Rich Bi«). Sb layer). The Bi*Sb-rich layer is present on the surface and/or interface of the Ag. alloy film. The B 2 -rich layer may be present only on the surface of the Ag alloy film, or only on the interface of the Ag alloy film, or on the surface and interface of the Ag alloy film. At this time, the surface of the Ag alloy film is outside the inside of the Ag film, and is not limited to the outermost surface or the outermost surface, and is from the outermost surface to the thickness (depth) of the thickness of the Ag alloy film of 1/4. Part (layer) is also included in the surface of the Ag alloy film, and the Bi·β Λ Sb layer is present in these portions (layers) (the case where the Bi·Sb layer is present on the surface of the Ag alloy film). • The interface of the Ag alloy film is such that when other films or layers are attached to the surface of the Ag alloy film (in the case of lamination), the interfaces of the other films or layers and the Ag alloy film are for the interface of the Ag alloy film. The meaning is the same as that of the surface of the above Ag alloy film, and is not limited to the interface or interface and its vicinity (the thickness of the interface from the interface to the thickness of the Ag alloy film of 1/4 (depth) - the part (layer) also The Bi.Sb-rich layer is present in the interface of the Ag alloy film in the interface (layer) (the case where the Bi·Sb layer is present in the interface of the Ag alloy film). The inside of the Ag alloy film refers to a portion (layer) between the surface or interface of the Ag alloy film to a thickness of 1/4 of the thickness of the Ag alloy film (depth ') and a thickness (depth) of 3 / 4 thickness. In the present invention, the Bi-rich Sb layer contains oxidized Bi and/or oxidized Sb as described above. The Bi·Sb-rich layer is composed of oxidized Bi and/or oxidized Sb in many cases, but is not limited thereto, and includes oxidized Bi and/or oxidized -37- 1265976 (34).

In the case where Sb is a main component, Bi may be oxidized and/or Sb may be present outside of Sb and/or Sb may coexist. Next, a preferred system of the third invention will be described. The inventors of the present invention performed the light reflection when the liquid crystal display element was manufactured by the inventor of the present invention. When the film was exposed to the air or the phenomenon caused by prolonged exposure under high temperature and high humidity during use after the manufacture, Ag was separately performed. The light-reflecting film (film thickness: 100 nm) was subjected to an environmental test at a temperature of 80 ° C and a relative humidity of 90% at a high temperature and humidity for 48 hours. As a result, the reflectance of the light-reflecting film was reduced by 7.0% after the environmental test - compared with the reflectance (wavelength 65 Onm) before the environmental test. The reason for the decrease in the reflectance (hereinafter referred to as 'the reflectance* decrease with time 〃) may be caused by factors such as growth of crystal grains or aggregation of Ag atoms as described in the above-mentioned prior art. Therefore, the inventors of the present invention have made great efforts to obtain the original light reflectance of Ag by preventing the decrease in the reflectance over time, and it is important to find an alloy component capable of removing or controlling these factors. • As a result of the investigation, the inventors have found that by containing Bi and/or Sb (one or two elements selected from Bi and Sb) in Ag, Ag can be suppressed while maintaining the original light reflectance of Ag. Aggregation or crystal grain growth inhibits the decrease in reflectance over time, so as to complete the present invention. Conventionally, instead of pure A g, an A g-based alloy has been used as a light-reflecting film, but as specified in the present invention, aggregation of Ag atoms is suppressed by adding Bi or Sb to Ag. The report of the growth of crystal grains of Ag has not appeared in the prior art. Inventors of the present invention have a light-reflecting film composed of an Ag-based alloy to which a rare earth-38·1265976 (35) element is added, in order to suppress the aggregation of Ag atoms or the growth of crystal grains of Ag (Japanese Patent Application No. 2002-01729) However, in the present invention, the light-reflecting film composed of the Ag-based alloy containing Bi and Sb has reflectance and durability thereon. * In the present invention, an Ag-based alloy containing Bi and/or Sb is used as the _ light-reflecting film, and since the reflectance is suppressed from decreasing with time and the high light reflectance is maintained, it is based on the technical idea clearly distinguished from the prior art. As will be described later, it is also possible to use a rare earth element such as Nd or Y which is inexpensive to be added to an Ag-based alloy containing Bi and/or Sb. Further, a ternary system or a quaternary or higher alloy containing a component of improving oxidation resistance, Au, Cu, Pt, Pd, and Rh, may also be used. Hereinafter, the present invention will be described in detail. In the present invention, as a light-reflecting film for a reflective liquid crystal display element or the like - in consideration of the problem of requiring reflection characteristics of visible light, the reflectance is measured at a wavelength of 65 0 nm to investigate the reflection characteristics. In the following description, the initial reflectance (%) 〃 refers to the reflectance (%) measured immediately after the formation of the light-reflecting film, and the size of the ruthenium is determined by the type and amount of the alloying element. In addition, the change amount (%) of the reflectance® is defined as ', the reflectance after the environmental test (%) - the initial reflectance (%) 〃, and the change over time (%) is a negative number. The reflectance after the environmental test is lower than the initial reflectance. If the light-reflecting film is formed of an Ag-based alloy containing Bi and/or Sb, it is possible to suppress crystal grain growth of Ag or aggregation of Ag atoms. In particular, the film formed by the sputtering method contains many defects such as atomic holes, so the Ag atoms are easily moved and diffused, and as a result, the Ag atoms are agglomerated, but the presence of Bi and Sb in the crystal of Ag suppresses Ag. Movement and diffusion suppress the growth of crystal grains of Ag or the aggregation of Ag atoms. -39- (36) 1265976 By adding a total of 0.01 atom% or more of Bi and/or Sb, it is possible to exhibit an effect of suppressing the growth of crystal grains of Ag or the aggregation of Ag atoms. However, as the amount of addition of these elements increases, the initial reflectance decreases or the resistivity increases. Therefore, a total of B i and/or S b is preferably added in a total amount of 4 atom% or less. In particular, when the liquid crystal display is used as both the reflector and the electrode, it is desirable to reduce the resistivity as much as possible. In other words, regarding the initial reflectance, if the total addition amount of Bi and/or Sb is within 2 atom%, Lu can maintain a high initial reflectance of 80% or more. On the other hand, regarding the specific resistance, the resistivity of the A1 alloy (Al — Ta, _ A1 — Nd, etc.) which is generally used for the wiring film of the liquid crystal display element is about 5 to 15 // Ω cm, and therefore, as in As shown in the later-described examples, if both Bi and Sb are within 1 · 8 at%, • a resistivity of 15 5 Ω cm or less equal to that of the Α 1 alloy wiring can be obtained. It is only used in a high melting point metal material such as Cr or Mo which is used for a liquid crystal display element wiring film in the same manner as the A1 alloy, and the specific resistance is used in the range of ～200 // Ω cm. Therefore, even if the addition amount of Bi and Sb exceeds 1.8 atom%, There is no problem with using ®. Therefore, a more preferable upper limit of the total amount of Bi and/or Sb is 2 atom%. On the other hand, as an environmental test for facilitating the reproduction of an environment in which Ag crystal growth or Ag atoms are aggregated, the light reflection film is allowed to stand under high temperature and high humidity at a temperature of 80 ° C and a relative humidity of 90% for 48 hours. Case • As long as the total amount of Bi and/or Sb exceeds 〇·〇5 at%, the difference between the reflectance [two initial reflectance] (%) before environmental test and the reflectance (%) after environmental test can be controlled. Within 1%, a more preferable lower limit of the total amount of Bi and/or Sb is 0.05 atom%. -40- (37) 1265976 The Ag-based alloy formed by the light-reflecting film of the present invention may further contain a rare earth element, particularly Nd and/or Y. Although the effect is small compared with Bi or Sb, Nd or Y also has the effect of improving the agglomeration resistance of Ag, - and Nd or Y is lower in cost than Bi or Sb, and therefore, if one, part of Bi or Sb is substituted, it can be lowered. cost. The total amount of addition of Nd and/or Y is suitably 〇·〇1 atom% or more. However, the addition of Nd or Y causes a decrease in initial reflectance or resistivity, and therefore, the total amount thereof is suitably 2 Φ atomic % or less, more preferably 1 atomic % or less (although no force is added to Ag in Ag and / or Sb, when only Nd and/or Y are added, the Ag resistance can be improved. However, as described later in the examples, there is a problem that the NaCl resistance cannot be improved.) - In addition, An and Cu may be added. , Pt, Pd, Rh, etc., to improve oxidation resistance. Although these elements do not suppress the effect of Ag agglutination, they have an effect of increasing chemical stability and suppress the decrease in reflectance over time. These elements increase the reflectance of the short-wavelength region (before and after 400 nm) in particular as the amount of addition increases. Therefore, the total amount is preferably 3 atom% or less, more preferably 2 atom% or less. A preferred system of the light-reflecting film of the present invention contains Bi and/or Sb, and if necessary, contains Nd, Y or Cu, Au, Pd, Rh, and Pt, and the remainder is substantially Ag, so that high can be obtained. The initial reflectance is , but other components than the above components may be added to the extent that the effects of the present invention are not affected. For example, Zn, Ti, Mg, Ni, or the like may be added to prevent chemical corrosion or reaction. Further, it is allowed to have a gas component such as Ar, 〇2, or Ν2, or an impurity contained in -41265976 (38) of the Ag-based alloy as a dissolution raw material. The light-reflecting film of the present invention can maintain a high reflectance for a long period of time, and is therefore suitable for use in a reflective liquid crystal display element. Further, since the light-reflecting film of the present invention is excellent in durability against structural changes such as crystal grain growth during heating, it is particularly suitable for a liquid crystal display device which is subjected to a heating step of usually 200 to 300 ° C in the production process. Further, since the light reflecting film has conductivity, it can be used as a reflective electrode of a reflective liquid crystal display device. Alternatively, it can be placed on the back of the transparent • electrode as a reflector. A well-known material such as a glass substrate or a plastic film substrate can be used as the electrode substrate used as the reflective electrode. Reflection, the substrate of the board can also make the same material. Further, it is possible to use both a light reflection film and a wiring film. • A light reflecting film is suitably formed on the above substrate or substrate by a sputtering method. Bi or Sb has a very small solid solution limit for Ag in a chemical equilibrium state, but a film formed by a sputtering method can achieve non-equilibrium solid solution according to the gas phase quenching inherent in the sputtering method, and thus forms A with other thin film formation methods. Compared with the case of the g-based alloy film, the alloy element is more likely to be uniformly present in the Ag matrix. As a result, the Ag-based alloy has improved oxidation resistance and can suppress the aggregation of Ag atoms. The film thickness of the light reflecting film is suitably 50 to 300 nm. The film thinner than 50 nm starts to transmit light' so the reflectance is lowered. On the other hand, if it exceeds '300 nm, although there is no problem in reflectance, it is not conducive to productivity or cost. At the time of sputtering, as a sputtering target (hereinafter sometimes referred to as "target"), a group selected from the group consisting of Bi: 〇·2 to 15 atom%, Sb: 〇.〇1 to 4 atom% is used. One or two of the same, and the amount of Bi in the sputtering target -42 - 1265976 (39) and the amount of Sb satisfying the following reproduction formula (3 - 1) of the Ag substrate can be obtained. Light reflecting film. 0·01' 0.000502nBi3 + 0.00987nBi2 + 〇.〇553nBi + nSb$ 4 . . . (3 - 1 ) • In the formula (3-1), nBi is the amount of Bi in the target (atomic %) , nSb is the amount of Sb (atomic %) in the target. Here, the reason why the Bi content in the target is larger than the Bi content in the light reflecting film is as follows. That is, when a light-reflecting film is formed by a sputtering method using a target composed of an Ag-based alloy containing Bi, the content of Bi in the light-reflecting film is reduced to a few % to several tens of % of the content of Bi in the film. The reason is considered to be that the difference between the melting points of Ag and Bi. ' is large' so that B i re-evaporates from the substrate during film formation, and the sputtering rate of A g is larger than the sputtering rate of B i , so bi It is not easy to be sputtered' and Bi· is more easily oxidized than A g. Therefore, only Bi is oxidized on the target surface without being sputtered or the like. The phenomenon that the content of the element in the light-reflecting film is significantly lower than the content of the element in the target is not observed in other Ag-based alloys such as Ag-Sb alloy and Ag-rare metal-based alloy. Therefore, the content of Bi in the target must be higher than the content of Bi in the target light reflecting film. For example, in order to obtain a light-reflecting film containing 0.005 to 0.4 atom% of Bi, it is necessary to consider the content of Bi which does not enter the light-reflecting film, and it is necessary to make the Bi content in the target 0 to 5 to 4 · 5 atom% (refer to the following description). Example 4). Further, the total amount of Bi and Sb contained in the above-mentioned "light-reflecting film" needs to be 〜1 to 4 atom%. Therefore, the Bi content and the Sb content in the target need to satisfy the formula (3 - 1 ). • Here, the enthalpy of each coefficient of nBi in the above formula (3 - 1) is -43-(40) 1265976, and the relationship between the Bi content in the target and the Bi content in the light-reflecting film is experimentally investigated. The result is approximate. As the target, an Ag-based alloy (Solvent-based Ag-based alloy) produced by a dissolution casting method is suitably used. The Ag-based underlying alloy is uniformly formed on the structure, so that the sputtering rate or the exit angle is constant, so that a light-reflecting film having a uniform composition of components can be obtained. When the oxygen content of the above-mentioned molten Ag-based alloy target is controlled to 10 Oppm or less, it is easy to maintain a constant film formation speed, and it is also possible to reduce the light T, the oxygen content in the stupid reflection film, and to improve the reflectance or the specific resistance. The reflective liquid crystal display device of the present invention suitably has the light-reflecting film of the present invention, and the configuration of the other liquid crystal display element is not particularly limited. Any configuration known in the field of liquid crystal display elements can be employed. The present invention will be described in detail below based on the embodiments, but the following examples are not intended to limit the invention, and modifications and modifications are intended to be included within the scope of the invention. [Embodiment] Embodiment 1 First, a method of measuring and evaluating each characteristic will be described below. [Preparation of Ag-based alloy thin film] A composite target in which various additive element chips were placed on a pure Ag sputtering target was used in a polycarbonate substrate (diameter: 50 mm, thickness: according to DC magnetron sputtering method). 1mm) pure Ag film (as a reflective film) or 15 nm (as a semi-transmissive reflective film) pure Ag (sample No. 1) -44 - 1265976 (41), Ag-Bi alloy (sample number 2 to 5) ), Ag—Sb alloy (sample No. 6 to 9), Ag—Bi—Nd alloy (sample No. 1〇~14), 岣, :Bi—Y alloy (sample No. 15 to 19), Ag—Sb - Nd alloy (sample No. 20 to 24), Ag - Sb - Y alloy (sample No. 25 to 29, ), Ag - Bi-Cu alloy (sample No. 30 to 34), Ag-Bi- Au sheet metal (g pattern No. 35~39), Ag-Sb-Cu alloy (sample No. 40~44), Ag-Sb- Au alloy (sample No. 45~49), Ag — — Nd — Cu gold (sample No. 50), Ag—Bi—Nd— Au alloy (sample No. 51), Ag—Bi—Y—Cu alloy (sample No. 52′), Ag—Bi—Y—Αιι alloy (sample No. 53), Ag-Sb- Nd - Cu alloy (sample No. 54), Ag - Sb - Nd - A u alloy (test sample No. 55), Ag-Sb-Y-Cu alloy (sample No. 56), Ag ~ Sb - Y - Α ιι alloy ( Sample No. 57), a film of Ag-Si alloy (sample No. 58), Ag, and a Sn alloy (sample No. 59). Then, the composition of these Ag-based alloy thin films was determined by ICP (Inductively Coupled Plasma) mass spectrometry. Next, the properties (thermal conductivity, reflectance, and durability) of the reflective film (film thickness: 100 nm) or semi-transmissive film (15 nm) were measured using each of the produced Ag-based alloy thin films. In particular, for the thermal stability in durability, the change in reflectance and surface roughness (average roughness) and crystal grain size before and after the high-temperature and high-humidity test were measured, and the chemical stability in durability was measured after the salt water immersion test. The appearance was changed, and the durability of each film was evaluated. 45-(42) 1265976 Example 1 1-1 [Measurement of thermal conductivity] The thermal conductivity of each of the films having a film thickness of 100 nm prepared as described above was measured by the following method. Using a 3 226 m Ω Hi TESTER manufactured by HIOKI, the sheet resistance Rs was measured according to the four-probe method, and the film thickness t was measured using an alpha-step 2 50 manufactured by TENCOR INSTRUMENTS, and the resistivity p (= chip resistance 値 RSX film was calculated). Thick t), according to the Wedman-Franz law, calculate the absolute temperature of 3 00K (and 27 ° C) of the thermal conductivity system number ^ ( = 2.51 X absolute temperature T / resistivity p). In the evaluation, it was judged that the thermal conductivity of the pure Ag film was 32 以上W/(m.K) of 256 W/(m·K) or more, which was determined to have a high thermal conductivity. The results are not shown in Tables 1 and 2. - From the table, 2, a film of pure Ag (-sample No. 1), Ag-Si alloy (sample No. 58), and sample numbers 2 to 4, 6 to 8, 1 satisfying the specified elements of the present invention are known. The Ag-bottom B alloy films of 〇~13, 15~18, 20~23, 25~28, 30~33, 35~38, 40~43, 45~48, 50~57 have high thermal conductivity. On the other hand, the sample Nos. 5, 9' 14, 19, 24, 29, 34, 39, 44, 49 of the Ag substrate alloy thin MS# &element; the addition of yttrium too much to obtain a given high thermal conductivity Also, a film of Ag-Sn alloy (sample No. 59) could not obtain a high thermal conductivity. The addition effect of Rh or Pd or Pt is the same as that of Cu or Αιι. -46- (43)1265976 Table 1

Thermal conductivity measurement results Sample number composition thermal conductivity [W / (m * K)] High thermal conductivity 1 pure Ag 320 〇 2 Ag - 0.005 atomic % Bi alloy 319 〇 3 Ag - 0.2 atomic % 8 丨 alloy 296 〇 4 Ag -0.4 at% Bi alloy 271 〇5 Ag-0.6 at% Bi alloy 247 X 6 Ag-0.005 at% 31) Alloy 319 〇7 Ag-0.2 at% 81) Alloy 292 〇8 Ag-0.4 at% Sb alloy 264 〇 9 Ag-0.6 at% Sb alloy 236 X 10 Ag-0.2 Atomic % Bi-0.01 Atom. /〇Nd alloy 296 〇11 Ag-0.2 Atomic %Bi-0.1 Atom °/(^(1 Alloy 294 〇12 Ag-0.2 Atomic % 8^0.5 Atomic °/(^(1 alloy 287 〇13 Ag-0.2 Atom ° /(^丨-2 atom ° / (^ (1 alloy 260 〇 14 Ag-0.2 atom% Bi-3 atom% Nd alloy 242 X 15 Ag-0.2 atom% Bi-0.01 atom% 丫 alloy 296 〇 16 Ag-0.2 Atomic atom% yttrium alloy 294 〇17 Ag-0.2 atom% Bi-0.5 atom% yttrium alloy 288 〇18 Ag-0.2 atom. /〇^-2 atom%Y alloy 262 〇19 Ag-0.2 atom%8丨-3 atom %Υ alloy 245 X 20 Ag-0.2 atom% Sb-0.01 atom% Nd alloy 292 〇21 Ag-0.2 atomic %81)-0.1 atom °/(^(1 alloy 290 〇22 Ag-0.2 atom%%31)-0.5 Atomic ° / (^ (1 alloy 283 〇 23 Ag-0.2 atom% 31) 2 atom ° / (^0 alloy 256 〇 24 Ag-0.2 atom% 81) -3 atom ° / (^ (1 alloy 238 X 25 Ag -0.2 atom%3b0.01 atom%丫 alloy 292 〇26 Ag-0.2 atom% Sb-0.1 atom% bismuth alloy 290 〇27 Ag-0.2 atom °/(^13-0.5 atom% bismuth alloy 284 〇28 Ag-0.2 Atomic % Sb-2 Atomic % Y Alloy 258 〇 29 Ag-0.2 Atomic Sb-3 Atomic Oxide Alloy 24 1 X -47- (44) 1265976 Table 2

Thermal conductivity measurement results Sample serial number Thermal conductivity [W/(m*K)] High thermal conductivity 1 Pure Ag 320 〇30 Ag-0.2 Atom 0/〇Bi-0.01 Atomic Cii Alloy 296 〇31 Ag-0.2 Atom Atom 0/〇Cu alloy 295 〇32 Ag-0.2 atom% Bi-0.5 atom% Cu alloy 290 〇33 Ag-0.2 atom% Bi-3 atom% Cu alloy 260 〇34 Ag-0.2 atom% Bi-4 atom% Οι alloy 248 X 35 Ag-0.2 Atom ο/〇Βί-0·01 Atomic % Au Alloy 296 〇36 Ag-0.2 Atomic % Bi-0·1 Atomic AA Alloy 295 〇· 37 Ag-0.2 Atomic Bi-0.5 Atomic % Au alloy 290 〇38 Ag-0.2 atom% Βί·3 atom% 八11 alloy 262 〇39 Ag-0.2 atom% Bi-4 atom%Au alloy 251 X 40 Ag-0.2 Atomic % Sb-0.01 Atomic % (11\1 Alloy 292 〇41 Ag-0.2 atom% Sb-0.1 atom% Cii alloy 291 〇42 Ag-0.2 atom% Sb-0.5 atom% Cu alloy 286 〇43 Ag-0.2 atom% Sb-3 atom% Cu alloy 256 〇44 Ag -0.2 atomic% Sb-4 atom 0/〇Cu alloy 244 X 45 Ag-0.2 atom% Sb-0.01 atom% Au alloy 292 〇46 Ag-0.2 atom% SWU atom 0/〇Au alloy 291 〇47 Ag-0.2 original 0/〇Sb-0.5 atom%Au alloy 286 〇48 Ag-0.2 atomic 0/〇Sb-3 atom%Au alloy 258 〇49 Ag-0.2 atomic 0/〇Sb-4 atom%Au alloy 247 X 50 Ag-0.2 Atomic % Bi-0.5 Atom o/〇Nd-0.5 Atom 0/〇〇! Alloy 281 〇51 Ag-0.2 Atom 0/〇Bi-0.5 Atomic %Nd-0.:5 Atomic %Au Alloy 281 〇52 Ag-0.2 Atom 0/〇Bi-0.5 atom% Υ·0·5 atom% Cu alloy 282 〇53 Ag-0.2 atom% Bi-0.5 atom% Υ-0·5 atom%Au alloy 282 〇54 Ag-0.2 Atomic % Sb_0. 5 Atomic % Nd - 0.5 Atom 0 / 〇〇 ! Alloy 277 〇 55 Ag - 0.2 Atomic % Sb - 0.5 Atomic % Nd - 0.5 Atomic AZ Alloy 277 〇 56 Ag_0.2 Atom 0 / 〇 Sb - 0.5 Atom ο / 〇 Υ-0·5 Atomic % Cii Alloy 278 〇57 Ag-0.2 Atomic % Sb-0.5 Atomic Oxide - 0 · 5 Atom 0 / 〇 Au Alloy 278 〇 58 Ag-0.2 Atomic % Si Alloy 265 〇 59 Ag-0.2 Atom %Sn alloy 248 X -48- (45) 1265976 Examples 1 to 2 [Measurement of reflectance] • The film thickness of 100 nm produced as described above was measured by Polar Kerr Scope ΝΕΟ ARK MODEL ΒΗ - 810 manufactured by Nippon Scientific Engineering Co., Ltd. " film versus visible light (wavelength 400~8 OOurn) reflectance. The high reflectance was evaluated as having a reflectance of 90.8% (wavelength 405 nm) and 92.5% (wavelength 650 nm) as a pure Ag film, which is 80% or more (wavelength 405 nm) and 88% or more (wavelength 650 nm). Lu reflectivity. Here, the wavelength 405 nm is the wavelength of the laser used for the next-generation optical disc, and the wavelength 65 Onm is the wavelength of the laser used for the DVD. The results are shown in - Table 3, 4 〇; from Tables 3 and 4, pure Ag (sample No. 1), Ag - Si - alloy (sample No. 58), Ag-Sn alloy (sample No. 59) The film and the sample numbers 2 to 4, 6 to 8, 1 0 to 13, 15 to 18, 20 to 23, 25 to 28, 30 to 33, 35 to 38, 40 to 43 satisfying the specified elements of the present invention. The 45.48, 50 >· 57 .Ag primer film has high reflectivity. On the other hand, in the Ag-based alloy thin films of sample Nos. 5, 9, 14, 19, 24, 29, 34, 39, 44, and 49, a given high reflectance could not be obtained due to the excessive addition of the alloying elements. The addition effect of Rh or Pd or Pt is the same as that of Cu or Au. -49 - (46)1265976 Table 3 Reflectance Measurement Results

Reflectance of sample composition to pure Ag [%] High inverse serial wavelength 405nm Wavelength 650nm Luminous rate 1 Pure Ag 90.8 92.5 〇2 Ag-0.005 atom ° / (^丨 alloy 90.7 92.5 〇3 Ag-0.2 atom% already 1 alloy 86.2 90.8 〇4 Ag-0.4 atom 0/〇Bi alloy 81.6 89.1 〇5 Ag-0.6 atom%Bi alloy 77.0 87.4 X 6 Ag-0.005 atom%31) alloy 90.7 92.5 〇7 Ag-0.2 atom%81?alloy 86.1 90.7 〇8 Ag-0.4 Atom 0/〇Sb Alloy 81.4 88.9 〇9 Ag-0.6 Atom 0/〇Sb Alloy 76.7 87.1 X 10 Ag-0.2 Atomic Bi-0.01 Atomic Nd Alloy 86.2 90.8 〇11 Ag-0.2 Atom o/ oBi-0.1 {^i%Nd alloy 85.9 90.7 〇12 Ag-0.2 atomic o/〇Bi-0.5 atom% can alloy 84.8 90.3 〇13 Ag-0.2 atom% Bi, 2 atom 0/〇Nd alloy 80.7 88.6 〇14 Ag -0.2 Atomic 0/Bai-3 ®i%Nd Alloy 78.0 87.5 X 15 Ag-0.2 Atomic Bi-0.01 Atomic Niobium Alloy 86.2 90.8 〇16 Ag-0.2 Atom 0/〇Bi-0.1 Atom 0/〇Y Alloy 85.9 90.7 〇17 Ag-0.2 atom% Bi-0.5 atom 0/〇Υ alloy 84.7 90.2 〇18 Ag-0.2 atom% Bi-2 atom% bismuth alloy 80.3 88.4 〇19 Ag-0.2 atom% Bi-3 atom% Υ Gold 77.4 87.2 X 20 Ag-0.2 atomic % Sb-0.01 atomic % Nd alloy 86.1 90.7 〇21 Ag-0.2 atomic % Sb-0.1 atomic % Nd alloy 85.8 90.6 〇22 Ag-0.2 atomic % Sb-0.5 atomic % Nd alloy 84.7 90.2 〇23 Ag-0.2 atom 0/〇Sb-2 atom% Nd alloy 80.6 88.5 〇24 Ag-0.2 atom 0/〇Sb-3 atom% Nd alloy 77.9 87.4 X 25 Ag-0.2 atom% Sb-0.01 atom% Y Alloy 86.1 90.7 〇26 Ag-0.2 atom% Sb-0.1 atom%¥ alloy 85.8 90.6 〇27 Ag-0.2 atom 0/〇Sb-0.5 atom%Y alloy 84.6 90.1 〇28 Ag-0.2 atom% Sb-2 atom%¥ Alloy 80.2 88.3 〇29 Ag-0.2 Atomic Sb-3 Atom 0/〇Y Alloy 77.3 87.1 X -50- (47)1265976 Table 4 Reflectance Measurement Results

Sample No. Composition Reflectance to Pure Ag [%] Local Reflectance Wavelength 405nm Wavelength 650nm 1 Pure Ag 90.8 92.5 〇30 Ag-0.2 Atomic Bi-0.01 Atom 0/〇Cu Alloy 86.2 90.8 〇31 Ag-0.2 Atom Atom %(^11 alloy 86.0 90.7 〇32 Ag-0.2 atom 0/〇Bi-0.5 atom 0/〇Cu alloy 85.3 90.4 〇33 Ag-0.2 atom%Bi-3 atom%Cu alloy 81.0 88.3 〇34 Ag-0.2 atom% Bi-4 atom% Cu alloy 79.3 87.5 X 35 Ag-0.2 atom% Bi-0.01 atom% Au alloy 86.2 90.8 〇36 Ag-0.2 atom% Bi-0.1 atom% Αιι alloy 86.0 90.7 〇37 Ag-0.2 atom% Bi- 0.5 atom 0/〇Au alloy 85.4 90.4 〇38 Ag-0.2 atom%Bi-3 atom%Au alloy 81.5 88.5 〇39 Ag-0.2 atom 0/〇Bi-4 atom 0/〇Au alloy 79.9 87.7 X 40 Ag_0.2 Atom 0/〇Sb-0.01 Atomic % Qi Alloy 86.1 90.7 〇41 Ag-0.2 Atom 0/〇Sb-0· 1 Atom o/oCu Alloy 85.9 90.6 〇42 Ag-0.2 Atomic Sb-0.5 Atomic Cu Alloy 85.2 90.3 〇43 Ag-0.2 atom 0/〇Sb-3 atom%Cu alloy 80.9 88.2 〇44 Ag-0.2 atom% Sb-4 atom% 〇1 alloy 79.2 87.4 X 45 Ag-0.2 atom% Sb-0.01 atom% Au alloy 86.1 90.7 〇46 Ag-0.2 atom 0/〇Sb-0.1 atom%Au alloy 85.9 90.6 〇47 Ag-0.2 atom% Sb-0.5 atom 0/〇Au alloy 85.3 90.3 〇48 Ag-0.2 Atomic % Sb-3 Atomic % Au Alloy 81.4 88.4 〇 49 Ag-0.2 Atomic % 31 > 4 Atom 0 / 〇Λ ι ι Alloy 79.8 87.6 X 50 Ag-0.2 Atom 0 / 〇 Bi-0.5 Atom 0 / 〇 Nd - 0.5 Atomic % Cu alloy 84.0 89.8 〇51 Ag-0.2 Atomic % Bi-0.5 Atomic % Nd-0.5 Atom 0/〇Au Alloy 84.0 89.9 〇52 Ag-0.2 Atom 0/〇Bi-0.5 Atom 0/〇Υ-0·5 Atom 0 /〇Cu alloy 83.9 89.8 〇53 Ag-0.2 atom%Bi-0.5 atom%Υ-0·5 atom 0/〇Au alloy 83.9 89.8 〇54 Ag-0.2 Atom 0/〇Sb-0.5 Atom 0/〇Nd-0.5 Atomic % Cii alloy 83.9 89.7 〇 55 Ag-0.2 Atomic % Sb-0.5 Atom 0 / 〇 Nd - 0.5 Atomic % Au Alloy 83.9 89.8 〇 56 Ag - 0.2 Atomic % Sb - 0.5 Atomic % Υ - 0 · 5 Atomic % 〇 1 Alloy 83.8 89.7 〇57 Ag-0.2 atom 0/〇Sb-0.5 atom%Υ-0·5 atom%Au alloy 83.8 89.7 〇58 Ag-0.2 atom%Si alloy 85.5 90.3 〇59 Ag-0.2 atom °/〇Sn alloy 85.0 89.9 〇-51 - 1265976 (48) Examples 1 to 3 [Durability Test 1: Measurement of Thermal Stability] A high-temperature and high-humidity test was performed on each film having a thickness of 100 nm in the measurement of the reflectance in the above Example 2 (temperature E degree 90%) RH - hold time 48 hours), again after the test. In the evaluation, the reflectance before and after the high-temperature and high-humidity test was 5% or less (wavelength 4〇5 nm) and 1% or less (the wave was judged to have high durability. The results are shown in Tables 5 and 6. From $5 6, it can be known that the Ag substrate film satisfying the requirements of the invention No. 2 to 57 has high durability pure g (sample No. 1), Ag-Si alloy (sample J Ag-Sn 〇 $ (sample The film of No. 59) cannot obtain the addition effect of '° Rh ^ Pd or Pt and the same effect as Cu or Au. The same is used! 80〇C—wet to measure the absolute length of reflectance change 6 5 Onm ) Sample order of the element. Relative to this number 58), given a high durability added effect phase -52- (49) 1265976

Table 5 Durability (thermal stability) evaluation results Sample number composition change before and after high temperature and high humidity test [%] Bureau durability wavelength 405nm Wavelength 650nm 1 Pure Ag -27.3 -3.0 X 2 Ag-0.005 atomic alloy-1.4 -0.8 〇3 Ag-0.2at%Bi alloy-0.7 -0.3 〇4 Ag-0.4at%Bi alloy-0.5 -0.2 〇5 Ag-0.6 atomic yttrium alloy -0.3 -0.1 〇6 Ag-0.005 atom%31) Alloy -1.6 -0.9 〇7 Ag-0.2 atomic %Sb alloy -0.8 -0.4 〇8 Ag-0.4 atomic %Sb alloy -0.6 -0.3 〇9 Ag-0.6 atomic %Sb alloy -0.4 -0.2 〇10 Ag-0.2 atom o/oBi-0.01 Atomic % Nd alloy -0.6 -0.2 〇11 Ag-0.2 atom 0/〇Bi-0.1 atom% Nd alloy-0.5 -0.1 〇12 Ag-0.2 atom% Bi-0.5 atom% Nd alloy-0.3 - 0.1 〇13 Ag-0.2 atom% Bi-2 atom% Nd alloy 0.0 0.0 〇14 Ag_0.2 atom% Bi-3 atom%·alloy 0.0 0.0 〇15 Ag-0.2 atom% Bi-0.01 atom 0/〇Y alloy- 0.6 -0.2 〇16 Ag-0.2 atom 0/oBi-0.1 atom% bismuth alloy -0.5 -0.1 〇17 Ag-0.2 atom. /〇Bi-0.5 atom%Υ alloy-0.4 -0.1 〇18 Ag-0.2 atom% Bi, 2 atom 0/〇Υ alloy 0.0 0.0 〇19 Ag-0.2 atom% Bi-3 atom 0/〇Υ alloy 0.0 0.0 〇 20 Ag-0.2 Atom 0/〇Sb-0.01 Atomic % Nd Alloy-0.7 -0.3 〇21 Ag-0.2 Atomic Sb-0.1 Atomic Nd Alloy-0.6 -0.2 〇22 Ag-0.2 Atom o/〇Sb-0.5 Atom %Nd alloy-0.4 -0.2 〇23 Ag-0.2 atom% Sb-2 atom 0/〇Nd alloy 0.0 0.0 〇24 Ag-0.2 atom% Sb_3 atom 0/〇Nd alloy 0.0 0.0 〇25 Ag-0.2 atom% Sb- 0.01 atom 0 / 〇 Y alloy - 0.7 - 0.3 〇 26 Ag - 0.2 atom 0 / 〇 Sb - 0.1 atom% bismuth alloy - 0.6 - 0.2 〇 27 Ag - 0.2 atom% Sb - 0.5 atom% bismuth alloy - 0.5 - 0.2 〇 28 Ag-0.2 Atom 0/〇Sb-2 Atomic Niobium Alloy 0.0 0.0 〇29 Ag-0.2 Atom 0/〇Sb-3 Atom 0/〇Υ Alloy 0.0 0.0 〇•53· (50) 1265976 Table 6

The sample number constitutes the reflectance change before and after the high temperature and high humidity test [%] High durability wavelength 405nm Wavelength 650nm 1 Pure Ag -27.3 -3.0 X 30 Ag-0.2 Atomic % Bi-0.01 Atom 0 /〇〇! Alloy-0.6 - 0.2 〇31 Ag-0.2 atom% Bi-0.1 atom 0/〇Cu alloy-0.5 -0.1 〇32 Ag-0.2 atom% Bi-0.5 atom% 〇1 alloy-0.4 -0.1 〇33 Ag-0.2 atom% Bi-3 Atomic %Cu alloy 0.0 0.0 〇34 Ag-0.2 atom%Bi-4 atom%〇1 alloy 0.0 0.0 〇35 Ag-0.2 Atomic % Bi-0.01 Atom 0/〇Au Alloy-0.6 -0.2 〇36 Ag-0.2 Atomic % Bi_0.1 Atom 0/〇Au alloy-0.5 -0.1 〇37 Ag-0.2 at% Bi-0.5 at% Au alloy-0.4 -0.1 〇38 Ag-0.2 atom 0/〇Bi-3 atom%Au alloy 0.0 0.0 〇 39 Ag-0_2 atomic 〇厥 4 atomic % Α ι ι ι 0.0 0.0 0.0 Ag 40 Ag-0.2 atom% Sb-0.01 atom% Cu alloy -0.7 -0.3 〇41 Ag-0.2 atomic % Sb-0.1 atom 0 / 〇 Cii alloy -0.6 -0.2 〇42 Ag-0.2 atom%81>0.5 atom% Cu alloy-0.4 -0·1 〇43 Ag-0.2 atom 0/〇Sb-3 atom%Cu alloy 0.0 0.0 〇44 Ag-0.2 atom% Sb-4 Atomic 0/〇Cu alloy 0.0 0.0 〇45 Ag-0.2 Atomic% Sb-0.01 Atom 0/〇Au Alloy-0.7 -0.3 〇46 Ag-0.2 Atomic Sb-0.1 Atomic Oxide Αιι Alloy-0.5 -0.2 〇47 Ag-0.2 Atomic Sb-0.5 Atomic % Au alloy -0.3 -0.1 〇48 Ag-0.2 atom% Sb-3 atom%Au alloy 0.0 0.0 〇49 Ag-0.2 atom 0/〇Sb-4 atom%Au alloy 0.0 0.0 〇50 Ag-0.2 Atom 0/〇Bi -0.5 Atomic % Nd - 0.5 Atomic % 〇 1 Alloy 0.0 0.0 〇 51 Ag - 0.2 Atomic % Bi - 0.5 Atomic O / 〇 Nd - 0.5 Atomic % Eight 11 Alloy 0.0 0.0 〇 52 Ag - 0.2 Atom 0 / 〇 Bi - 0.5 Atomic % Υ · 0.5 Atomic % Cu alloy 0.0 0.0 〇 53 Ag - 0.2 Atomic % Bi - 0.5 Atom 0 / 〇 Y - 0.5 Atomic % Au Alloy 0.0 0.0 〇 54 Ag - 0.2 Atomic % Sb - 0.5 Atomic % Nd - 0.5 Atom 0/〇Cu alloy 0.0 0.0 〇55 Ag-0.2 Atom 0/〇Sb-0.5 Atomic % Nd-0.5 Atomic % Au Alloy 0.0 0.0 〇56 Ag-0.2 Atom 0/〇Sb-0.5 Atomic % Y-0.5 Atom 0/ 〇Cu alloy 0.0 0.0 〇57 Ag-0.2 Atom 0/〇Sb-0.5 Atom ο/〇Υ-0·5 Atom 0/〇Au Alloy 0.0 0.0 〇58 Ag-0.2 Atomic Ni alloy-19.9 -2.1 X 59 Ag -0.2 atomic % Sn alloy -18.4 -1.8 X •54- (51) 12659 76 Examples 1 to 4 [Durability Test 2: Measurement of Chemical Stability] Each of the films having a film thickness of 15 nm prepared as described above was subjected to a salt water immersion test (saline concentration: 0.05 mol / 1 NaCl, brine temperature: 2 (TC, immersion time: 5 minutes), the appearance change of the film after the test was visually observed. At the time of evaluation, it was judged that the appearance change such as discoloration or peeling was not observed to have high durability. The results are shown in Tables 7 and 8. As is apparent from Tables 7 and 8, the Ag-based alloy film of Sample Nos. 2 to 57 which satisfies the predetermined elements of the present invention has high durability. Relative to this pure Ag (4 sample number 1), Ag-Si alloy (sample number 58),

The film of Ag Sn gold (sample No. 59) could not obtain a given high durability half. The addition effect of R h or P", d or Pt is the same as that of Cu or Au. -55- (52) 1265976

Appearance change after salt immersion test of Ag film. Composition change after salt immersion test High durability 1 Pure Ag X 2 Ag-0.005 at% Bi alloy 4τττ 1ΙΙΓ > i \\ 〇3 Ag-0.2 Atomic 0/〇Bi alloy and / \ \\ 〇4 Ag-0.4 atom%Bi alloy 4ττΤ JuL ^\\\ 〇5 Ag-0.6 atom%Bi alloy 4ητ ΊΠπ j\\\ 〇6 Ag-0.005 atom% Sb alloy >fnT ΊιΠ J \ w 〇7 Ag-0.2 atomic% Sb alloy MJ \ w 〇8 Ag-0.4 atom% Sb alloy 4mi illi: y 〇9 Ag-0.6 atom% 81) alloy MJ ^ \\ 〇10 Ag- 0.2 atom% Bi-0.01 atom% Nd alloy>fnT it ΓΓ y \ \\ 〇11 Ag-0.2 atomic o/〇Bi-0.1 atom% Nd alloy 4mi ifil! 〇12 Ag-0.2 atom% 81-0.5 atom% Nd alloy >fnr tttt j\\\ 〇13 Ag-0.2 atom%Bi-2 atom 0/〇Nd alloy 4nt tttt yi 〇14 Ag-0.2·atomic%Bi-3 atom%_alloy 4nt ΠίΓ 〇15 Ag- 0.2 atom% Bi-0.01 atom 0/〇Y alloy-frrr ΙιΤΓ y \,, 〇16 Ag-0.2 atom ο/oBi-Ol atom 0/〇Υ alloy 4rxr 1111: 〇17 Ag-0.2 atom% Bi-0.5 atom Tantalum alloy 4rvr tlir j \ \\ .〇18 Ag-0.2 atom%Bi_2 atom%Υ alloy>fnT IIIK j \ \\ 〇19 Ag-0.2 atom 0/〇Bi-3 atom%Υ alloy M jw\ 〇20 Ag-0.2 Atomic % Sb-0.01 Atom 0/〇Nd Alloy 1111- 〇21 Ag-0.2 Atom o/〇Sb-0.1 Atom 0/〇Nd Alloy 4mi llTi ^ w\ 〇22 Ag-0.2 Atomic Sb-0.5 Atom 0/〇Nd alloy>frrr lilt 〇23 Ag-0.2 atom% Sb-2 atom% Nd alloy>fnr ttiT J \ w 〇24 Ag-0.2 atom%31>3 atom °/(^(1 alloy jnn jw \ 〇25 Ag-0.2 atom% Sb-0.01 atom% Y alloy λχτΐ ΠΤΓ J \\\ 〇26 Ag-0.2 atom% Sb-0.1 atom% bismuth alloy>fnT 1Ι1Γ, 〇27 Ag-0.2 atom% Sb- 0.5 atom% niobium alloy yfnr tttr: j \ \\ 〇28 Ag-0.2 atom% Sb-2 atom% niobium alloy IMi j \\\ 〇29 Ag-0.2 atom% Sb-3 atom% niobium alloy >fnr iiir j \ \\ 〇-56- (53) 1265976

Appearance change of Ag-based film after salt water immersion test

Sample No. Composition Change after salt immersion test High durability 1 Pure Ag X 30 Ag-0.2 Atom o/〇Bi-0.01 Atom 0/〇Cii Alloy 4m: 1 π Γ 〇31 Ag-0.2 Atomic Bi- 0.1 atom%. !!合金>fnT. 无〇32 Ag-0.2 Atom 0/〇Bi-0.5 Atom 0/〇Cii Alloy 4rrr JILL 〇33 Ag-0.2 Atom 0/〇Bi-3 Atom 0/〇Cii Alloy 4nr ΙΙΙΓ / 〇 34 Ag-0.2 atom 0/〇Bi-4 atom%Cu alloy 4vrr juH, N 〇35 Ag-0.2 atom% Bi-0.01 atom% Αιι alloy M j \\\ 〇36 Ag-0.2 atom% Bi-0.1 atom% Au alloy and J ΪΝΝ 〇37 Ag-0.2 atom% Bi-0.5 atom% Αιι alloy TTttt 〇38 Ag-0.2 atom 0/〇Bi-3 atom% Αιι alloy 赃川, 〇39 Ag-0.2 atom%Bi-4 atom 0/—alloy 4rrr ΙιΓΓ J \ w 〇40 Ag-0.2 atom%31>0.01 atom%〇1 alloy>fnT- ιιΠΓ 〇41 Ag-0.2 atom% Sb-0.1 atom%Cu alloy>fnr 〇42 Ag- 0.2 atom% Sb-0.5 atom% Cu alloy 4rrr. It it: J \ 〇43 Ag-0.2 atom 0/〇Sb-3 atom%Cu alloy 4ttt ΙΠΕ j\\\ 〇44 Ag-0.2 atom% Sb-4 atom 0/〇Cu alloy>fnT tin JV 〇45 Ag-0.2 atom% Sb-0.01 atom%Au alloy 4\rr. Ι11Γ j \\\ 〇46 Ag-0.2 atom% Sb-0.1 atom%Au alloy MJV 〇47 Ag-0.2 atomic% Sb-0.5 atomic% eight 11 Alloy 4ml j \\\ 〇48 Ag-0.2 Atom 0/〇Sb-3 Atom 0/οΑιζ Alloy Sister 49 Ag-0.2 Atom 0/〇Sb-4 Atomic AA Alloyiffi j \\\ 〇50 Ag-0.2 Atomic % Bi - 0.5 Atomic % Nd - 0.5 Atom 0 / 〇 Cu alloy > frrr Ulc JV 〇 51 Ag - 0.2 Atomic % Bi - 0.5 Atomic % Nd - 0.5 Atom 0 / 〇 Au Alloy sister , 〇 52 Ag - 0.2 Atomic 〇/(^-0.5 atom% Υ-0·5 atom% 〇1 alloy 4ml 1ΠΓ J w\ 〇53 Ag-0.2 atom% Βί-0·5 atom% Υ-0·5 atom%Au alloy inL· ztttC 〇54 Ag-0.2 atom% Sb-0.5 atom% Nd-0.5 atom% Cii alloy 4rrT illl: J 〇55 Ag-0.2 atom% 31)-0·^ atom 0/〇^(1-0.5 atom% eight 11 alloy >fnr till y » \N 〇56 Ag-0.2 Atom 0/〇Sb-0.5 Atomic %Υ-0·5 Atom 0/〇Cu Alloy 4tni 111! J i 〇57 Ag-0.2 Atom 0/〇Sb-0.5 Atomic % Υ - 0 · 5 Atom 0 / 〇 Au Alloy MJ \ \\ 〇 58 Ag - 0.2 Atomic % Other alloys have X 59 Ag - 0.2 Atomic % Sn alloy with X - 57 - (54) 1265976 Examples 1 to 5 [Durability Experiment 3: Measurement of Thermal Stability] For each film having a film thickness of 100 nm produced as described above, Dlgltal was used.

Nanoscope melon a scanning probe microscope manufactured by Instruments • Surface morphology observation and surface roughness (average roughness: Ra) were measured according to the AFM (Atomic Force Microscope) mode. Then, the film subjected to the AFM mode measurement was subjected to a high-temperature and high-humidity test (temperature 80 ° C - humidity 90% RH - holding time 48 hours), and surface morphology observation and surface roughness were again performed after the test (average roughness: Ra) Determination of). In the evaluation, the average thickness before and after the high-temperature and high-humidity test was less than 1 n m, which was judged to have a local durability. The results are not in Table 9, 10. -, - From Tables 9 and 10, it is known that the sample of the sample which satisfies the specifications of the present invention - No. 2 to 57, the Ag-based alloy film has high durability. On the other hand, a film of pure Ag (sample No. 1), Ag-Si alloy (sample No. 58), and Ag-Sn alloy (sample No. 59) could not obtain a given high durability. The addition effect of Rh or Pd or Pt is the same as the addition effect of Cu or Au. -58- (55)1265976

Average thickness of Ag film before and after high temperature and high humidity test

The sample number constitutes the average thickness before and after the high temperature and high humidity test [nm] High durability test before the test 1 Pure Ag 4.18 7.33 X 2 Ag-0.005 atom%Bi alloy 0.63 0.93 〇3 Ag-0.2 atom%Bi alloy 0.58 0.61 〇4 Ag-0.4 atom%Bi alloy 0.55 0.58 〇5 Ag-0.6 atom 0趟 alloy 0.52 0.54 〇6 Ag-0.005 atom%315 alloy 0.65 0.95 〇7 Ag-0.2 atom °/〇Sb alloy 0.58 0.63 〇8 Ag- 0.4 atom% Sb alloy 0.56 0.59 〇9 Ag-0.6 atom% Sb alloy 0.54 0.57 〇10 Ag-0.2 atomic % Bi-0.01 Jli% Nd alloy 0.58 0.60 〇11 Ag-0.2 atom% Bi-0.1 atomic 0/〇Nd alloy 0.55 0.59 〇12 Ag-0.2 atom% Bi-0.5 atom 0 alloy. 0.52 0.56 〇13 Ag-0.2 atom 0/〇Bi_2 atom% Nd alloy 0.45 0.48 〇14 Ag-0.2 atom% Bi-3 atom 0 alloy 0.44 0.48 〇15 Ag-0.2 Atom 0/〇Bi-0.01 Atom 0/〇Y Alloy 0.57 0.60 〇16 Ag-0.2 Atom 0/〇Bi-0.1 Atomic Oxide Alloy 0.56 0.59 〇17 Ag-0.2 Atomic Bi-0.5 Atom %Y alloy 0.53 0.58 〇18 Ag-0.2 atom% Bi-2 atom% bismuth alloy 0.47 0.53 〇19 Ag-0.2 atom% Bi-3 original Υ%Υ alloy 0.45 0.52 〇20 Ag-0.2 Atom 0/〇Sb-0.01 Atomic %Nd Alloy 0.58 0.62 〇21 Ag-0.2 Atom 0/〇Sb-0.1 Atom 0/〇Nd Alloy 0.56 0.60 〇22 Ag-0.2 Atom %Sb-0.5 atom% Nd alloy 0.53 0.58 〇23 Ag-0.2 atom% Sb-2 atom% Nd alloy 0.47 0.50 〇24 Ag-0.2 atom% Sb-3 atom% Nd alloy 0.47 0.49 〇25 Ag-0.2 atom% Sb -0.01 Atom 0/〇Y Alloy 0.58 0.63 〇26 Ag-0.2 Atomic Sb-0.1 Atomic Oxide Alloy 0.55 0.61 〇27 Ag-0.2 Atomic Sb-0.5 Atomic Oxide Alloy 0.54 0.60 〇28 Ag-0.2 Atom 0/ 〇Sb-2 atom 0/〇Υ alloy 0.46 0.54 〇29 Ag-0.2 atom%81> 3 atom% bismuth alloy 0.45 0.53 〇-59- (56) 1265976

Table 10 Average thickness of Ag film before and after high temperature and high humidity test Sample number composition Average thickness before and after high temperature and high humidity test [nm] High durability test before test 1 Pure Ag 4.18 7.33 X 30 Ag-0.2 Atom 0/ 〇Bi-0.01 Atomic %Cii Alloy 0.59 0.93 〇31 Ag-0.2 Atom 0/〇Bi-0.1 Atomic %Cii Alloy 0.58 0.90 〇32 Ag-0.2 Atomic %Bi-0.5 Atomic % (1111 Alloy 0.56 0.86 〇33 Ag-0.2 Atomic % Bi-3 Atomic % Cu alloy 0.55 0.75 〇 34 Ag-0.2 Atomic % Bi-4 Atomic % Cu alloy 0.54 0.73 〇 35 Ag-0.2 Atomic % Bi-0.01 Atomic AA Alloy 0.59 0.94 〇36 Ag-0.2 Atom /oBi-0.1 Atomic % Au Alloy 0.57 0.89 〇37 Ag-0.2 Atom*%Bi-0.5 Atom*%Au Alloy 0.56 0.84 〇38 Ag-0.2 Atom 0/〇Bi-3 Atom 0/〇Au Alloy 0.54 0.76 〇39 Ag-0.2 atom% Bi-4 atom 0/〇Au alloy 0.53 0.75 〇40 Ag-0.2 atomic%Sl>0.01 atomic 0/〇Cii alloy 0.59, 0.95 〇41 Ag-0.2 atom% Sb-0.1 atom% 〇1 alloy 0.58 0.91 〇42 Ag-0.2 atom% Sb-0.5 atom% Cii alloy 0.57 0.88 〇43 Ag-0.2 atom% Sb-3 atom% Cii alloy 0.56 0 .78 〇44 Ag-0_2 Atom 0/〇Sb-4 Atom 0/〇〇! Alloy 0.54 0.77 〇45 Ag-0.2 Atomic % Sb-0.01 Atom 0/〇Au Alloy 0.58 0.94 〇46 Ag-0.2 Atomic Sb- 0.1 atom% Au alloy 0.58 0.90 〇47 Ag-0.2 atom% Sb-0.5 atom% Au alloy 0.57 0.86 〇48 Ag-0.2 atom 0/〇Sb-3 atom%Au alloy 0.57 0.79 〇49 Ag-0.2 atom% Sb_4 atom o/oAu alloy 0.55 0.77 〇50 Ag-0.2 atom% Bi-0.5 atom% Nd-0.5 atom% Cii alloy 0.50 0.55 〇51 Ag-0.2 Atomic % Bi-0.5 Atom 0/〇Nd-0.5 Atomic %Au Alloy 0.51 0.56 〇52 Ag-0.2 Atom o/〇Bi-0.5 Atom ο/〇Υ-0·5 Atom 0/〇Cii Alloy 0.52 0.57 〇53 Ag-0.2 Atomic Bi-0.5 Atom 〇Υ/〇Υ-0·5 Atomic % Au alloy 0.51 0.55 〇54 Ag-0.2 Atomic % Sb-0.5 Atom 0/〇Nd-0.5 Atomic % Cii Alloy 0.52 0.58 〇55 Ag-0.2 Atomic % Sb-0.5 Atomic % Nd-0.5 Atom 0/〇Au Alloy 0.53 0.60 〇56 Ag-0.2 Atom 0/〇Sb-0.5 Atom 0/〇Υ-0·5 Atomic %〇! Alloy 0.52 0.59 〇57 Ag-0.2 Atomic % Sb-0.5 Atomic Υ-0.5 Atomic AA Alloy 0.54 0.59 〇 58 Ag-0.2 Atomic % Si alloy 0.68 1.17 X 59 Ag-0.2 atom% 311 alloy 0.79 1.25 X -60 - (57) 1265976 It can be known from the results of Table 1~1 0 above that this sample is satisfied. Samples 2~4, 6~8, 10~ 13, 15~18, 2〇~23 30~33, 35~38, 40~43, 45~48, 50~57: Gold film has high thermal conductivity, high reflectivity, high durability and full performance. Especially in the A g - B i alloy (sample No. 3), the metal halogen Nd (sample number 1〇~14) or the addition of γ number 1 5~1 9 ), or added (: 11 (sample number) 3〇~ Au (g pattern number 35 to 39) is improved in durability compared with Ag-Bi alloy ( ). Also added to the Ag-sb alloy ( , ) is a rare earth metal element Nd (sample No. 2) 〇力□ γ (sample number 2 5~2 9 ), or adding -41 to 44 of c 11) or adding Au (sample number 45 to 49) is more durable than gold (sample number 7) Increased in nature. Further add N d and C11 in gold (δ pattern number 3) (samples add Nd and Au (sample number 5 1 ), add γ and ® sample number 5 2 ), add | γ and Compared with Au (sample No. 5 3 ) - alloy (sample No. 3), durability and further improvement of Ag-Sb alloy (sample No. 7) were added with Nd and Cu, No. 5 4 ), and Nd and Au were added. (Sample No. 5 5 ), Cu (Sample No. 56), and addition of Y and Au (Testing sympleced with Ag-Sb alloy (Sample No. 7), durability was advanced. Example 2 Example i Invention Prescribed, 25 to 28, Ag bottom The surface has a rare earth added (sample order 3 4) or added sample number 3 sample number 7 ~ 24) or added (sample number Ag - Sb combined with A g - B i vocal number 50), Cu (Try with Ag - Bi. Similarly, increase in the sample order by adding Y and _ No. 57. -61 - 1265976 (58) Using a sputtering material whose main component is Ti, according to the sputtering method (in Ar and In a mixed atmosphere of oxygen (a colorless float glass, a plate thickness of 3 mm, and a size of 2 cm X 4 cm), a titanium oxide film (film thickness: 30 nm) was formed as a base material for each test. Using the above-mentioned substrate, an Ag alloy film (Ag alloy film for electromagnetic wave shielding) having a composition shown in Table 12 was controlled to have a film thickness on the underlayer (titanium oxide film) of the above-mentioned substrate according to a sputtering method (in an Ar atmosphere). In the case of i〇nm, the film is formed. In this case, a 5x5mm plate-shaped sheet (made of an alloy component such as Bi) is placed on the pure Ag target as a sputtering target. • The above Ag alloy film (and pure Ag) After film formation, the sputtering target of the main component of Ti is used again, according to the sputtering method (in Ar and oxygen) In the atmosphere, titanium oxide (film thickness: 20 nm) was formed as a protective layer on the above Ag alloy film, thereby obtaining an electromagnetic wave mask in which a titanium oxide/Ag alloy film/titanium oxide three-layer structure film was formed on a transparent substrate. On the other hand, in order to analyze the composition of the Ag alloy film, a composite target for forming an Ag alloy film is used, and a sputtering method is used according to the same conditions as when the Ag alloy film is formed. Only an Ag alloy film was formed on the glass, and the composition of the film was determined by the ICP method. Further, an Ag alloy film* was formed for the electromagnetic wave mask obtained by the film formation, and the sheet resistance (resistance 値) and visible light transmittance were measured. Further, after performing a high-temperature and high-humidity test [placed in an atmosphere of 85 t and 90% RH (relative humidity) for 48 hours], the presence or absence of aggregation of Ag was measured, and the sheet resistance was also measured. At this time, the sheet resistance was determined by the four-probe method. For Ag-62-(59) 1265976 agglutination is observed with the naked eye and optical microscope (multiplier: 2〇〇). The visible light transmittance is based on the method specified in JIS R3 106, and the measurement is performed for the above-mentioned A g alloy film. The body was subjected to salt water immersion (N a C 1 concentration·· 0 · 0 5 m ο 1 /liter, immersion time··15 minutes) _ The discoloration and peeling state were observed. The results of the above-mentioned δ-type test temples and the composition of the above Ag alloy film are shown in Table 10. • Comparative Example 2 - 1 * An Ag alloy film formed body in which an Oxide/Ag alloy film/oxidized/structure film was formed on a transparent substrate was obtained in the same manner as in the case of Example 2-1. The composition of the Ag alloy film is different from that of the case of the one, as shown in Table 2. That is, the alloy component is any one of Nb, Sn, Cu-Al, and Zn. Further, only the Ag target is formed into a film of a pure Ag film, and a pure Ag film formed on a transparent substrate is formed of a titanium/pure Ag film/titanium oxide three-layer structure film. 11) 〇 The above Ag alloy film forming body and pure The same test was carried out for the same method as in the case of the Ag film forming apparatus. Further, in the same manner as in the case of the examples, only Ag ' was formed on the float glass, and the composition of the film was determined by the ICP method. The results of these tests and the like and the above-mentioned Ag alloy film group are shown in Table 12 and Table 11. analysis. Stain test, visual inspection together, condition, titanium three-layer application 2 Nd, In using pure oxide (table, according to the alloy film together; 63- 1265976

One-to-one evaluation results salt water immersion test stripping deer stag deer stag deer stag deer scorpion discoloration (yellow) X □ 〇〇〇〇〇〇 〇〇〇〇〇〇 〇〇〇〇〇〇 1 § § ON 00 v 〇§ 00 p· 阻抗 film impedance (Ω/α) After Ag agglutination test (N 卜 T-H < N inch CO 卜 m Ag agglutination test m 00 rH CN cn 00 cn (N , S ύ S\l fe « si t W. < X □ 〇〇〇〇〇〇 〇〇〇 〇〇 o 〇〇 Adding element amount (atomic %) 1 1—Η Ο Ο Ο CN rH 〇On rH 〇cs O o rH 0.009 so rH rH O (N (N 〇^HG) inch 〇〇r«H constitutes pure Ag Ag-Bi Ag-Sb Ιέ (N inch in 00 Os o F-H CN in Comparative Example 1 Example 1 -64 - (61) 1265976 (61)

- Evaluation results Salt water immersion test Peeling discoloration (yellowing) X □ □ XXXX Visible light transmittance (%) r- jo VO JQ 2 VO sheet impedance (Ω/ο) Ag agglutination test two m cn 00 cn mi Ag agglutination Before the test 1__ VD VO m Release 1 1 1 ! 岖< 〇XXXXXX Add element quantity source %) 〇0.40 0.92 1 0.88 o Os o ο Composition 5 X) Z Old P % < s Test No. I 00 ON Comparative Example 1 -65- (62) 1265976 The results of Example 2 - 1 and Comparative Example 2 - 1 g test N 〇. 1 7 (A g - In) , 18 (Ag - N b ) , 19 (Ag -

The Sb), 20 (Ag-Cu), 21 (Ag-Al), and 22 (Ag-Zn)-related electromagnetic wave mask Ag alloy film formations were referred to in Comparative Example 2-1. Further, the test Νο·1 relates to a pure Ag film formed body (Ag film composition: pure Ag) ’ is referred to in Comparative Example 2-1. These Ag alloy film formations and pure Ag film formations can be seen with the naked eye on the surface of the transparent substrate (glass) after high temperature and high humidity test, and Ag aggregation is confirmed (X in Table 12 and Table 11). Express). • For this reason, the test N 〇 · 2 to 16 of the invention according to Example 2-1 of the present invention was used for the electromagnetic alloy mask for the Ag alloy film formation body after the high temperature and high humidity test, and the white spot was not visible to the naked eye. Further, as a result of observation by an optical microscope at a multiple of 200 times, in the Ag alloy film formation, the amount of Bi and/or Sb in the Ag alloy film was less than 0.04 atom%, and the test Νο·2, Νο. 3, Νο· In the Ag and alloy film formations involved, it is confirmed that there are 15 to 25 white spots (indicated by Δ in Table 1 1 ® ). However, in addition to the amount of the alloying element (addition element) in the film: the white point of the Ag alloy film formed body of 5% by weight or more is 10 or less (indicated by 〇 in Table 11). On the other hand, as the amount of addition of Bi or Sb increases, the display sheet resistance (resistance) increases, and the visible light transmittance tends to decrease. In general, the Ag alloy film forming body for electromagnetic wave shielding is preferably a light transmittance of not less than the viewpoint of ensuring visibility and visibility. In addition, in general, it is sufficient to ensure the infrared ray shielding sheet resistance as long as it is approximately 40 Ω / □, but the upper limit of the sheet resistance to ensure radio wave masking is -66 - 1265976 (63) is approximately 30 〇 / port. (The chip resistance is the physical unit of the impedance ratio (Ω.m) divided by the film thickness phase *. The physical unit is Ω. Here, / □ is attached to Ω to indicate the film impedance. The film impedance is also expressed by Ω / □. Therefore, from the viewpoint of ensuring the infrared ray opacity, the amount of addition of Bi or Sb is suitably 10 atom% or less, and 'from the viewpoint of ensuring radio wave masking, Bi or Sb The amount of addition is suitably 5 atom% or less. • The results of measuring the sheet resistance of each Ag alloy film formation after the high-temperature and high-humidity test, and the case of the Ag alloy of the test No. 1 in Comparative Example 2-1, the film formation body, according to the high-temperature and high-humidity test piece The resistance is greatly increased. However, in the case of the Ag alloy film-form of the test No. 2 to 15 according to the embodiment of the present invention, the rise of the sheet resistance is small, and all of them are almost 40 Ω / □ or less. In the salt water immersion test, the Ag alloy film formed body of the test No. 16 (Comparative Example 2-1) which is good in the high temperature and high humidity test (indicated by 〇 in Table 12) (Ag alloy film composition: Ag - Nd) discoloration (indicated by X in Table 12) and Ag alloy film formation (Ag alloy film composition: containing Bi or Sb) of the test Νο·2~15 according to the embodiment 1. In the case of the case, the discoloration is small (indicated by Δ and 〇 in Table 1 1 , wherein in particular, Bi or Sb: 0.05 at% or more is completely invisible to discoloration (indicated by 〇 in Table 11). Further, the embodiment of the present invention 2—1 The Ag alloy film formed body did not cause peeling at all. Example 2 - 2 -67- (64) 1265976 A target having a main component of A1 (aluminum) is used as a primer layer on a transparent substrate (colorless float glass, plate thickness: 3 mm, size: 2 cm x 4 cm) according to a sputtering method (in a mixed atmosphere of Ar and oxygen) A film-forming aluminum oxide film (_ film thickness: 20 nm) was used as a substrate for each test. The composition shown in Table 13 was used on the underlayer (alumina film) of the above substrate according to a sputtering method (in an Ar atmosphere) using the above substrate. The Ag alloy film (the Ag alloy film for electromagnetic wave mask) is controlled to have a film thickness of about 15 nm to form a film. In this case, it is composed of pure Ag, Ag - 0.2 at% Sb, Ag - 0.1 at% S b . A 5 x, 5 mm plate-shaped sheet (composed of Bi, Au, Cu, or Pd) is placed as a 'sputter target' on a molten target (made by a vacuum dissolution method) - the above Ag alloy film (and pure Ag film) After the film formation, a sputtering target having a main component of A1 was used again, and alumina (film thickness: 40 nm) was formed as a protective layer on the above Ag alloy film by a sputtering method (in a mixed atmosphere of Ar and oxygen). This results in the formation of aluminum oxide / Ag ® alloy film / alumina three layers on a transparent substrate. The electromagnetic wave mask of the structural film is formed of an Ag alloy film. On the other hand, in order to analyze the composition of the Ag alloy film, the composite ruthenium for forming the Ag alloy film is used, and the same conditions as those for forming the Ag alloy film are used. In the shot method, only the Ag alloy film was formed on the float glass, and the composition of the film was determined by the *ICP method. In addition, the Ag alloy film formed by the electromagnetic wave mask obtained by the film formation was used to measure the sheet resistance (resistance 値), visible light transmittance. Further, after performing the high-temperature and high-humidity test [in the atmosphere of 85 ° C, 90% RH (relative humidity) - 68 - (65) 1265976 for 240 hours], the surface of the glass is enlarged by the projector to condense the Ag agglutination point ( White point) number. Tablet resistance was also measured. The sheet resistance is determined by the four-probe method. Visible light transmittance - measured by the method specified in JIS R3 106. The results of these tests and the like and the composition of the above Ag alloy film are shown in Table 13. -Comparative Example 2 - 2 The same pure * formed as Test No. 1 of Comparative Example 2 - 1 was produced, and the same test as in the case of Example 2-3 was carried out. The results are shown in Table 13. Results of Example 2-2 and Comparative Example 2-2 Test No. 23 relates to a pure Ag film formation (Ag film group Ag), which is referred to in Comparative Example 2-2. After the high-humidity test of the pure Ag film formation body, it was confirmed by the naked eye that a plurality of white spots (Ag dots) were generated, and according to the high-temperature and high-humidity test, the sheet resistance was greatly increased. For this, the electromagnetic wave of the test No. 24 was covered. When the cover is made of an Ag alloy body (Ag alloy film composition: Ag - 0.19 atom%), the number of Ag agglomeration points is about 10, which is extremely small. And * Can not see the increase in the sheet resistance according to the high temperature and high humidity test. The electromagnetic wave mask of Test Nos. 25 to 34 is composed of an Ag alloy film-shaped Ag alloy film: Ag - Bi or Sb - Au, Cu or Pd) is involved in the embodiment 2 - 2, and these Ag alloy film forming bodies are in the same manner. At this time, it is based on a joint

Ag film test. A white point is formed in the agglomerated ruthenium film which is pure at the local temperature (and almost adult (in the present invention, white-69-(66) 1265976 points (aggregation point of Ag) produces a number of Ags than the above test Νο. 24 There are few cases of the alloy film forming body, and it can be known from Table 13 that the number of white spots is also decreased as the amount of addition of An, Cu or Pd is increased. • In addition, in the examples 2 - 1 and 2 - 2 For Bi and Sb, each of them is added separately, but in the case of simultaneous addition, the same tendency as in the case of Examples 2 - 1 and 2 - 2 can be obtained. Further, in Example 2 - 2, Cu, Au, Pd, Among Rh, Ru, Ir, and Pt, Au, Cu, and Pd are added individually, but in the case of simultaneous addition, the same tendency as in the case of Example 2-4 can be obtained. Further, Au, Cu, In the case where the elements '(Rh, Ru, Ir, Pt) other than Pd are added and the force is added simultaneously [], the same tendency as in the case of the second embodiment can be obtained. Example 2 - 3, Comparative Example 2 - 3 Using a target whose main component is ITO, according to high-frequency sputtering (in Ar atmosphere), polyphenylene terephthalate with a thickness of 70/m On the acid glycol (PET) ® film, an ITO film having a thickness of 40 nm was formed by sputtering, and Ag - 0.5 at% Bi target (hereinafter referred to as 〇.5Bi-T) was used to form Ag - Bi having a thickness of 15 nm. Further, an ITO film having a thickness of 40 nm was formed by a sputtering method from the laminated film (hereinafter referred to as ITO / Ag - Bi alloy film (using 0.5 Bi - T, film thickness: 15 nm) / ITO three-layer film) The surface was etched with Ar' ion beam, and composition analysis was performed in the film thickness direction according to XPS. As a result, it was confirmed that Bi was concentrated on the interface between the ITO film and the Ag-Bi alloy film on the outermost layer (the layer farthest from the PET film). From the narrow-field spectrum of the concentrated Bi, it was confirmed that Bi was oxidized. -70-1265976 (67) On the other hand, in the above laminated film, the film thickness and the number of layers of each layer were also the same, except that the target composition was A. g — 1 · 5 atom% B i (hereinafter referred to as 1.5Bi—T) is a laminated film formed by forming an Ag—Bi alloy film (hereinafter referred to as ITO/Ag-Bi alloy film (using 1.5Bi—T, film thickness) 15nm) / ITO three-layer film) and the target composition of Ag - 2.0 atom% Bi (hereinafter referred to as 2.0Bi-T) as Ag - Bi alloy Film-formed laminated film (hereinafter referred to as ITO/Ag-Bi alloy film (using 2.0Bi-T, film thickness 15 nm • ) / ITO three-layer film). In addition, film formation uses Ag-1 atom% in the above film formation. A Pd target was used instead of a laminated film of an Ag-Bi alloy film (hereinafter referred to as - ITO/Ag - 1 at% Pd alloy film (film thickness: 15 nm) / three-layer film of ITO) (film of a comparative example). Further, a laminated film having a film thickness of only 2 nm of an Ag-Bi alloy film formed by using 0.5Bi-T (Ag-0.5 atom% Bi target) in the film formation described above (hereinafter referred to as ITO/Ag-Bi) was produced. Alloy film (using 〇.5Bi—T, film thickness 2 nm)/three-layer film of ITO). For the five films thus produced, that is, ® (1) ITO/Ag-Bi alloy film (using 0.5Bi-T, film thickness 15nm) / ITO three-layer film (2) ITO/Ag-Bi alloy film (used 1.5Bi—T, film thickness 15nm) / ITO three-layer film (3) ITO/Ag—Bi alloy film (using 2.0Bi—T, film thickness ^ 15nm) / ITO three-layer film (4) ITO/Ag— 1 atom% Pd alloy film (film thickness I5nm) / IΤ 三 three-layer film) (5) ITO/Ag-Bi alloy film (using 0.5Bi — T, film thickness -71 - (68) 1265976 2nm) / ITO The three layers of the film were each immersed in a brine having a concentration of 〇5 mol/L, and the agglutination of Ag was observed with an optical microscope (multiple: 200 times). • As a result, the film of (4), that is, the ITO/Ag-1 atomic% Pd alloy film (film thickness: 15 nm) / three-layer film of ITO) (the film of the comparative example) was subjected to immersion for 75 hours to start generation of Ag on the surface. Agglomerated white spots, but in contrast, (1) to (3) films, ie, ITO/Ag-Bi alloy films • (using 〇.5Bi—T, film thickness 15 nm) / ITO three-layer film (this Film involved in the invention, ITO/Ag-Bi alloy film (using 1.5Bi-T, film thickness)

, 15 nm) / ITO three-layer film (film according to the embodiment of the invention), ITO_ /Ag-Bi alloy film (using 2.0Bi-T, film thickness 15nm) / ITO - three-layer film (invention example) The film involved) did not show any change after immersion in 150 hours, and showed excellent salt water impregnation resistance. The film of (1) to (3) and the film of (4) have the same film thickness (thickness of 15 nm).

The film of ® (5), that is, the ITO/Ag-Bi alloy film (using 0.5Bi-T, film thickness 2nm) / ITO three-layer film, after 60 hours, began to produce white spots on the surface indicating Ag gagulation, with the above The film of (1) is inferior to the salt water impregnation property, but this is because the film thickness of the Ag-Bi alloy film is thin (film thickness: 2 nm). Such a film of (5) has a film thickness of 2 nm of the Ag-Bi alloy film, but a film of (4) of an Ag-1 atom% Pd alloy film having a thickness of 15 nm thicker than that of the film (ITO/Ag- The atomic % Pd alloy film (film thickness 15 nm) / ITO three-layer film) is almost equal in time to start generating white spots indicating agglomeration, and the salt water impregnation resistance is not much different -72-(69) 1265976, almost the same. As described above, in the case of immersion in brine (concentration 〇.5mol/L), the film of (5) (ITO/Ag-Bi alloy film (using 0.5Bi-T, film thickness 2nm) / ITO three-layer film) is 60 After a lapse of hours, white spots indicating agglomeration were started on the surface, so that even if the Ag-B i alloy film was thinner than 2 nm, the desired salt water impregnation resistance could not be obtained. At this time, it is necessary to set the film thickness of the A g—Bi alloy film to 3 nm or more. Example 2 - 4, Comparative Example 2 - 4 ITO film / Ag - Bi alloy film / ITO film was sequentially formed by sputtering on a PET (polyethylene terephthalate) film having a thickness of 70 / zm. Ag—Bi alloy film/ITO film/Ag—Bi alloy film/ITO film, laminated film of film-forming ITO film and Ag—Bi alloy film. At this time, a target of Ag - 0.25 at% Bi (hereinafter referred to as 0.25 Bi-T) was used for the production of the Ag-Bi alloy film. Further, the film thickness of each layer was formed so that the ITO film was 20 nm, and the Ag-Bi alloy film was 10 nm. The surface of the laminated film (hereinafter referred to as a seven-layer film of ITO / Ag - Bi alloy film (using 0.25Bi - T, film thickness: 10 nm)) was etched with Ar ion beam, and composition analysis was performed in the film thickness direction according to XPS. It was confirmed that Bi was concentrated on the interface between the ITO film and the Ag—Bi alloy film on the outermost layer (the layer farthest from the PET film). Further, it was confirmed from the narrow-field spectrum of the concentrated Bi that Bi was oxidized. On the other hand, in the above laminated film, the thickness of each layer was made the same as the number of layers, except that a laminated film of Ag-Bi alloy film portion was replaced by Ag-1 atom% Pd - 1.7 atom% Cu alloy film (hereinafter referred to as ITO / Ag — —73— 1265976 (70) A film of a 1 atom% Pd-1.7 atom% Cu alloy film (film thickness: 10 nm) (film of a comparative example). For the two films thus produced, namely, (a) ITO/Ag-Bi alloy film (using 〇.25Bi-T, 10 nm), a seven-layer film (b) ITO/Ag-1 atomic Pd-1.7 The seven-layer film of the atomic %Cu alloy film thickness lOnm was each immersed in a brine having a concentration of 55 mol/L, and the agglutination of Ag was observed by optical display (multiple: 200 times). As a result, the film of (b), that is, the ITO/Ag-1 atom% pd.v atomic% Cu alloy film (film thickness i〇nm), a seven-layer film (comparative example-film) was immersed for 40 hours. On the surface, a film indicating the Ag agglutination is produced, but in contrast, the film of (a), that is, the ITO/Ag-Bi alloy film is 0.25 Bi—T, and the film thickness is 10 nm (the embodiment of the present invention) The film) did not show any change after immersion for 100 hours, showing excellent salt water impregnation. In the films of (a) to (b), the film of the alloy film was the same (film thickness: 10 n m ). Seven layers of film thickness (. micromirror -1.7 and white point (so that the thickness of the difference is -74- 1265976

e 撇 働 可见光 可见光 可见光 可见光 可见光 可见光 On On On On On On On On On On On On On On On On On AG AG AG AG AG AG AG AG AG AG On On On On On On On On On On On On On On On On On On On On卜v〇Os r- Ό (N Os 00 (Μ 1- 尚温局 Wet test white point occurs a number of 00 〇 \ Ο 00 Ο inch 00 inch o 〇o Ο 1 add element amount Μ, other 1 1 m ο ON寸 inch ο rH m o' om 10.0 卜 cm' 卜 Gs 丨丨丨Μ BI/SB 1 0,9 0.19 0.19 0.19 0.19 0.19 0.19 0.21 0.21 0.21 0.21 Composition 5 Ag-Bi- Ag-Bi· Ag-Bi- &quot O Ph Ag-Sb-Ag-Sb-Test No. cn CN 00 CN (N cn m Comparative Example 2 Example 2 -75- (72) 1265976 A 5 mm x 5 mm Bi or Sb metal piece was placed on a pure Ag target, In the DC magnetron sputtering method, a sample of the composition of Table 1 of the thickness ι ηιη of Table 1 was prepared on a glass substrate. The composition of the film was another 'film under the same conditions. A sample with a thickness of 1 m is measured by IC p - mass spectrometry (SPQ - 8 000 manufactured by Seiko Instruments Inc.). Specifically, a test of l〇〇nig or more is used. As a pretreatment, it was dissolved in a solution of nitric acid: pure water = 1 :1, and it was heated on a hot plate at 200 ° C. The sample was completely dissolved and then cooled for analysis. The target size was ¢) = 100 mm. The size of the glass substrate is Φ = 50 mm. The main film formation conditions are: true air vacancy: 6·67 X 1 0 — 4Pa, Ar gas pressure at film formation: 267.267Pa, substrate • Temperature: 25°C, The distance between the target and the substrate was 55 mm. ^ The reflectance of each sample was measured immediately after film formation using a visible ultraviolet spectrophotometer (manufactured by Shimadzu Corporation). In addition, the environmental test of these samples was measured by the above spectrophotometer (temperature 8 (TC, The reflectance after 90% relative humidity and 48 h) was evaluated for the amount of change in reflectance before and after the environmental test. The surface roughness before and after the environmental test was measured by atomic force microscopy (AFM), and the surface roughness before and after the environmental test was evaluated. The amount of change in the degree was further measured by a salt water immersion test (NaCl: 0.05 m〇l / L, 15 minutes), and the degree of discoloration of the reflective film and whether the light-reflecting film was peeled off from the substrate were visually observed to evaluate the NaCM resistance. Comparative Example 3 - 1 The metal piece disposed on the pure Ag target was replaced with Nd, In, Nb or Sn of Bi or Sb of the above Example 3-1, in the same manner as the above Example 3-1 -76- (73) 1265976 The same film forming conditions were used to prepare a chalky alloy film as shown in Test No. 1 3 to 16 of Table 1, and the same evaluation as in Example 3-1 was carried out. The evaluation results of Example 3-1 and Comparative Example 3-1 are shown in Table 1. Table 14. As shown in Example 3-1 of Table 14, the addition of Bi or Sb was compared with the pure A g film (_No.l) (Test Nos. 2 to 12 can significantly suppress the reflectance before and after the environmental test. The amount of change and the amount of change in the surface. For the addition amount of Bi or Sb, although 〇.〇1 atom# can see the effect (test N.· 2, 8), especially 〇·〇5 atom% is effective (test N 〇 · 3 to 7, 9 to 1 2 ). Further, after the salt water is immersed, it can be seen that the yellowing of the light reflecting film or the peeling of the light reflecting film from the substrate disappears according to the addition of Bi or Sb. For this reason, as shown in Comparative Example 3-1 of Table 14, Ag - Nd showed good change in the reflectance before and after the suppression of the environmental test, but there was no N a C 1 durability ( Test n ο · 1 3 ). In addition, A g — B Ag — Nb and Ag - Sn are not effective in suppressing the amount of change in surface roughness (test ο ο ̄ 1 4 ～1 6 ). Example 3 - 2 A composite target of 5 mmx. of Bi, Cu, Au, Nd or Y metal sheets is placed on a target of pure Ag or Ag - 〇. 2% Sb, and is formed under the same film forming conditions as real 3-1. The results of the same evaluations for the samples as in Example 3-1 are shown in Table 15. The comparisons in Table 5 were repeated to reproduce the tests in Table 14 ι0·; ι and 4. J Ag is shown in the test) When the thickness % is also on the test, the test is equilibrated. Although the result is In, the case is usually 5 mm lower, and the method is 77- 1265976 (74). It can be known that the surface roughness is improved by adding Nd or γ to the Ag-Bi. The amount of change (test Ν〇 · 18, 19). It is known that the addition of Cu or Au to Ag-Bi or Ag-Sb is an effect of improving the amount of change in the rate of radiation (the test No. 19 to 24). Example 4 Comparison of the amount of Bi in the sputtering target and the amount of Bi in the film In order to compare the amount in the sputtering target and the film formed using the film, a sputtering target having the composition shown in Table 16 was used to form an Ag substrate. film. A gold film (Ag-Bi alloy film) was formed on a transparent substrate (in a glass atmosphere, a thickness of 3 mm, and a size of 2 cm x 4 cm) by a sputtering method (in an Ar atmosphere), and the film thickness was controlled to be about 15 nm. A molten target (made by a solution) composed of an Ag-containing alloy containing Bi was used as a sputtering target. The amount of Bi in the dissolved target was confirmed based on the analysis. The A g-based alloy portion of the obtained film was used in an amount of 10 m g or more, and dissolved in a solution of nitric acid: pure water of 1:1. Then, it was confirmed by heating on a hot plate at 200 ° C to completely dissolve the sample and then cooled, and the amount of Bi contained in the sample was measured by mass spectrometry (SPQ-8000 manufactured by Seiko Instruments Inc.). The results are shown in Table 16. , can enter the okay, reduce the situation

Bi-containing alloy, colorless float Ag. At this time, the vacuum solution is determined (for the sample, it is placed in the ICP - film -78-1265976

Inch lm evaluation results salt water immersion test elk soil 壊壊壊壊 chain 壊挨璀 discoloration (yellow) X □ 〇〇〇〇〇 □ 〇〇〇〇 X □ □ X 腾 ε G G ϋ % (N oi V〇(N cn cn ο 卜 · οο Η Η 〇 & Ν Ν Ν Ν Ν ΓΛ ΓΛ VO ΓΛ Os' Os inch · Τ VO VO surface roughness (nm) variation "C-D1 ΠΊ 卜Og 〇g O ψ·^ ο ο Ο ο s Ο Ο Ο g Ο S o 〇oso § o »Λ> rn ο Η 卜 (Ν After the environmental test [D] m 卜 00 (N o 〇Ό 〇Ό ( Ν Ο Ό Ό· Ο 00 rs Ο fH 〇 〇 (N Ό 〇 VO VO 〇Ό 〇 · · Ν Ν Ν Ν Ν d & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & & VD 〇Ο ΓΟ ν〇ο 3 Ο ^-Η CN (Ν On Ο m Ό O' r〇〇o (N 〇VC CO F—Η (Ν »/ί reflectance (%): wavelength 4〇〇nm change Β Β Α Α Γ Ί Ί Ί — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — — <ri 00 <N ss inch US 00 inch 00 00 inch<Ν Ό Ο cn 00 (N ss* inch » T) 00 OO inch (N o 00 ΓΛ ro 00 m 00 ο G< te burial 1» 〇〇§ inch Os oo (N 00 OO <N Ό* oo (Ν 00 ΓΟ (Ν ν〇 inch Os OO ( N OO OO (N \6 00 <N 〇\ VO 00 00 SS* oo ΓΛ oo oo Add element (atomic %) 1 F-H 〇oo On 〇Os Ο ο (Ν fH ΓΟ 0.009 sor-H ( N 〇oo f—^ 〇ΓΛ inch o' o o' (Ν On Ο 00 00 o 43⁄4 pure Ag Ag-Bi Ag-Sb -a Z body t 43 c cn body 1 (N cn inch Ό oo ON o rH (NH inch > Α) 实施 Implementation 1 - Η Compare 舾汹 __: x , «Sports dance: V, €3 relatives target: 〇: (舾2n€)M (Fang-79- (76) 1265976

Evaluation result Resistivity (μΩαη) m (Ν· cn ΓΟ Not determined not measured ^r ΓΛ Η (Ν r^' ro οο (Τ) Surface roughness (nm) Variation [C-D1 mouth 0.06 0.01 -0.03 0.02 0.01 0.09 0.03 0.06 0.03 After environmental test [D] ΓΟ 0.71 0.49 0.56 0.70 0.71 0.72 0.68 0.70 0.62 Alcohol FT δ release (Ν 0.6 0.65 0.48 0.59 0.68 0.70 0.63 0.65 0.64 0.59 Reflectance (%): wavelength 400nm variation fB-Al - 27.3 -0.8 〇v〇〇ο -0.2 ο Ο ο ο ο ο After the environmental test, the net 63.5 85.4 84.7 84.8 85.5 85.7 87.2 86.0 85.8 00 m „ wins < S te 吆m transport » 90.8 86.2 00 85.4 86.0 85.9 87.5 86.1 85.8 ι—Η 00 Adding element amount KL·Others 1 1 卜〇^Τ) 〇Os Ο ο ο ΓΟ ο ο ο m 丨1丨Bi/Sb 1 0.19 0.19 0.19 0.19 0.19 0.19 0.20 0.20 0.20 Composition 1 Pure Ag S T3 •—PQ >rs Ρ U • ν-Ν PQ D < SU PQ < 3 Ελ ο U Ελ body — inch 00 〇\ (Ν Example 2 -80- (77) 1265976 Table 1 6 i-type serial number The amount of Bi in the composition film of the sputtering target [atomic % 1 1 Ag - 0.01 atomic % Bi alloy < 0.001 2 Ag - 0.04 original %Bi alloy <0.001 3 Ag - 0.05 atomic % Bi alloy 0.005 4 Ag - 0.20 atomic % Bi alloy 0.011 5 Ag - 1.41 atomic % Bi alloy 0.056 6 Ag - 4.50 atom% Bi alloy 0.398 7 Ag - 7.00 atom% Bi alloy 1.02 8 Ag^ 14.3 atomic % Bi alloy 3.82 9 Ag - 22.9 atom % Bl · alloy 9.93 10 Ag - 40.8 atom % Bi alloy 27.2 It can be seen from Table 16 that the amount of Bi in the Ag alloy film is less than the amount of Bi in the target. The Bi content in the sputtering target of the Ag alloy film in order to obtain the desired Bi content is determined in consideration of the relationship of the Bi content in the sputtering target and the film formed using the film. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of composition analysis in the film thickness direction of the X-ray photoelectron spectroscopy of an Ag-Bi alloy film, which shows the relationship between the sputtering time and the composition of the X-ray photoelectron spectroscopy. Fig. 2 shows the results of Bi narrow-spectrum measurement of the Ag-Bi alloy film by X-ray photoelectron spectroscopy, which shows the relationship between the binding energy and the strength. -81 -

Claims (1)

(1) 1265976 X. Patent Application Area 1. An Ag-based alloy thin film comprising at least one element selected from Bi or Sb, and the total content of Bi and Sb is 0.005 to 10 atomic %. The Ag-based alloy film of the first aspect, wherein the Ag-based alloy film has a thickness of 3 to 300 nm. 3. The Ag-based alloy film according to claim 1, wherein the _ contains an Ag-based alloy having a total content of Bi and Sb of 0.005 to 0.40 atom%. 4. The Ag-based alloy film according to claim 1, wherein the Ag-based alloy further comprises at least one element selected from the group consisting of C'u, Au, Rh^, Pd or Pt, and the elements The total content of the Ag-based alloy film according to the first aspect of the patent application is as follows, which comprises an Ag-based Lu alloy having a total content of Bi and Sb of 0.01 to 10% by atom. 6. The Ag-based alloy film according to claim 1, which comprises an Ag-based alloy having a total content of Bi and Sb of 0.01 to 4% by atom. -82-