1263686 因此，相變化光碟，係將Ge-Sb_Te 一 兩側，以硫化鋅，氧化物（ZnS.Si〇 ) “⑽薄膜層之 夾持’並設置料金反射膜，而構成L層構；^點介電質 其中之反射層與保護層，除要求增大1 部與結晶部之反射率差、即光學機能外，亦要：之非晶質 之耐濕性及防止其受熱而變形之功能、及記錄:二錄薄膜 件之功能（參照非專利文獻1 )。 “才二制熱條 如此，針對高熔點之介電保護層之 及冷卻造成之熱的反覆應力具有耐性 =2汁溫 會影響反射膜及其他部分，並要求其本身;=熱影響不 要f之強減。這代表著介電保護層具有重 丄地，丨电保護層，係藉由一般 法，俜#用ns 版久鍍法而形成。該濺在 向，：； 理：將正極與陰極構成之基板與綱 ; “生“％境氣氛中施加高電壓於該基板與靶4 二：'場產生’此時，電離之電子與惰性氣體產生碰丰 =電毁，此電毁中之陽離子碰撞於乾（陰極）… 而破出乾之構成原子，此飛出之原子附著於對向之基板名 面而形成膜。 〆昆以住，一般主要使用於可覆寫型光資訊記錄媒體之保 ^之ZnS-Sl02，其於光學特性、熱特性、與記錄層之密 “生:皆具有優異之特性，而廣泛被使用。 以往係使用如此之ZnS-Si〇2等之陶瓷濺鍍靶形 成數百〜數千A左右之薄膜。 K63686 但是，此等材料， 故無法以直流濺鍍裝 (RF)裝置。 靶之體 置進行 電成 阻率（bulk resistlvity)高， 膜’ 一般係使用高頻濺鍍 而’此高頻濺鍍（RF ) 還具錢鑛效率低、耗電量大二’不僅裝置本身為高價’ 多數缺點。 工制複雜、成膜速度慢等 人’马提昇成膜速度而施加高 升而使聚碳酸酯製基板產生變形之門土反’皿义上 之Μ P P @ 小之問題。又，由於ZnS-SiO. m而導致生產量低或成本增加之問題。 ‘ 波二為代表之可覆寫…，除雷射波長短 =外’亦強烈追求增加覆寫次數、高容量化、及高速 s己錄化，但上述ZnS_S〗〇2材料亦有其他問題。 么此係光資訊記錄媒體之覆寫次數變差。其原因之… =因』zns-sI〇2之硫成分，擴散至被保護層之Zns彻2夹 持之έ己錄層材中。 一言又，為了大容量化、高速記錄化，而將具有高反射率、 回導熱性之純Ag或Ag合金使用於反射層材，但因反射層 =以鄰接於保護層Zns_si02之方式配置，故由於 &成分之擴散，同樣使純Ag或Ag合金反射層材腐蝕劣化， 而成為引起光資訊情報媒體之反射率等特性變差之要因。 為防止此等硫成分之擴散，於反射層與保護層、記錄 層與保護層間，設置以氮化物或碳化物為主成分之中間 層’但因積層數增加，亦造成生產量低或成本增加之問題。 因此，不使用ZnS、亦即不含硫成分之透明導電材料 1263686 被提出（參照專利文獻丨及2)。但是，專利文獻丨，有 光學特性及非晶質性變差方面之問題；專利文獻2，有無 法付到足夠之成膜速度、非晶質性變差方面之問題。 非專利文獻1 : 「光學」雜誌，20卷1號，第9〜15 頁。 專利文獻1 :日本專利特開2000_256059號公報。 專利文獻2 ·曰本專利特開2〇〇〇_256〇61號公報。 【發明内容】 本發明係關於濺鍍靶及其製造方法、以及光資訊記錄 媒體用薄膜（特別是作為保護膜使用）及其製造方法，係 抓用含SiO2系氧化物之材料，鄰接之反射層、記錄層不易 發生劣化，而且能密合性良好地高速成膜。藉此，而以提 昇光資訊記錄媒體之特性及大幅改善生產性為目的。 為解決上述問題，本發明人等經努力研究結果得知， 將保⑺層材ZnS-Si〇2’置換成不含琉化物而僅含氧化物之 材料、，，能確保與同程度之光學特性及非晶質安定 性’並且能夠高速成膜、且改善光資訊記錄媒體之特性、 提昇生產性。 本發明基於上述見識，提供： 及3價以上元 υ—種濺鍍靶，係以氧化錫、氧化鋅、 於X線繞射圖中 比係 12/11=0.:14 素之氧化物為主成分；其特徵在於，氧化錫相（ιι〇)之 峰值強度II、與氧化錫以外之氧化物或複合氧化物相存在 2Θ = 15〜40°範圍内之最大峰值強度12，其 如1)中之濺鍍靶，當該Μ為Sn以外 1263686 之 3價以上元素之場合，Sn/(Sn+Zn + M) = 0.4〜〇 9、1263686 Therefore, the phase change optical disc is made of a layer of Ge-Sb_Te, with zinc sulfide, oxide (ZnS.Si〇) "(10) film layer sandwiched" and a gold-reflecting film is formed to form an L-layer structure; In the dielectric layer, the reflective layer and the protective layer are required to have a difference in reflectance between the one portion and the crystal portion, that is, an optical function, and also an amorphous moisture resistance and a function of preventing deformation due to heat. And record: the function of the second film member (refer to Non-Patent Document 1). "The two heat strips are so resistant to the high-melting-point dielectric protective layer and the thermal stress caused by the cooling. Reflect the film and other parts, and ask for its own; = heat effect do not strongly reduce f. This means that the dielectric protective layer has a heavy-duty, anti-electrical protective layer, which is formed by the general method, 俜# using the ns version of the permanent plating method. The sputtering is in the direction of::;; the substrate consisting of the positive electrode and the cathode; "a high-voltage applied to the substrate and the target 4 in the "%" atmosphere: "field generation" at this time, ionized electrons and inert gases The collision occurs. The cation in the electric smash collides with the dry (cathode). The dry constituent atoms are broken, and the flying atoms adhere to the opposite surface of the substrate to form a film. 〆 〆 以 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , In the past, a ceramic sputtering target such as ZnS-Si〇2 was used to form a film of several hundred to several thousand A. K63686 However, these materials cannot be used as a direct current sputtering (RF) device. The body has a high bulk resistlvity, and the film 'is generally used for high-frequency sputtering. 'This high-frequency sputtering (RF) also has low efficiency and high power consumption. 'Not only the device itself is expensive. ' Most of the shortcomings. The complexity of the system, the slow film formation rate, etc. 'The horse lifts the film forming speed and applies the high rise, which causes the polycarbonate substrate to deform. The door is the opposite of the PP @小之 problem. Again, Due to ZnS-SiO.m, the production volume is low or the cost is increased. 'Poly 2 is representative of overwriting..., except for the short wavelength of the laser = externally, it also strongly seeks to increase the number of overwriting, high capacity, and high speed. s recorded, but the above ZnS_S〗 〇 2 materials also have other The reason for this is that the number of overwrites of the information recording medium is deteriorated. The reason is... The sulfur component of zns-sI〇2 is diffused into the Zns of the protected layer. In other words, in order to increase the capacity and record at high speed, a pure Ag or Ag alloy having high reflectivity and thermal conductivity is used for the reflective layer, but the reflective layer is disposed adjacent to the protective layer Zns_si02. Therefore, due to the diffusion of the & component, the corrosion of the pure Ag or Ag alloy reflective layer is also deteriorated, which causes the deterioration of the characteristics such as the reflectance of the optical information medium. In order to prevent the diffusion of these sulfur components, the reflection Between the layer and the protective layer, the recording layer and the protective layer, an intermediate layer containing nitride or carbide as a main component is provided. However, due to an increase in the number of layers, the production amount is low or the cost is increased. Therefore, ZnS is not used, that is, A transparent conductive material 1263686 containing no sulfur component has been proposed (see Patent Documents 2 and 2). However, the patent document 丨 has problems in optical characteristics and amorphous properties; Patent Document 2 cannot be sufficient. Film formation Problem of amorphous poor aspects of Non-Patent Document 1: Journal of "optics", vol. 20 No. 1, 9~15 page. Patent Document 1: Japanese Patent Laid-Open Publication No. 2000-256059. Patent Document 2: Japanese Patent Laid-Open Publication No. Hei. No. 256-61. SUMMARY OF THE INVENTION The present invention relates to a sputtering target, a method for producing the same, and a film for an optical information recording medium (particularly used as a protective film) and a method for producing the same, which are obtained by using a material containing an SiO 2 -based oxide, adjacent to a reflection The layer and the recording layer are less likely to be deteriorated, and the film can be formed at a high speed with good adhesion. In this way, the purpose of improving the characteristics of the optical information recording medium and greatly improving the productivity are aimed at. In order to solve the above problems, the inventors of the present invention have made an effort to study the results, and to ensure that the (7) layer material ZnS-Si〇2' is replaced with a material containing no telluride and only an oxide, thereby ensuring the same degree of optics. Characteristics and amorphous stability' and high-speed film formation, improved characteristics of optical information recording media, and improved productivity. Based on the above findings, the present invention provides: and a trivalent or higher elemental sputtering target, which is a tin oxide, zinc oxide, and an oxide in the X-ray diffraction pattern of 12/11=0.:14 The main component; characterized in that the peak intensity II of the tin oxide phase (ιι), the maximum peak intensity 12 in the range of 2Θ = 15~40° with the oxide or composite oxide phase other than tin oxide, such as 1) In the case of a sputtering target, when the yttrium is a divalent or higher element of 1,263,686 other than Sn, Sn/(Sn+Zn + M) = 0.4 to 〇9,
Zn/(Sn + Zn + M)二0·1 〜0.6、M/(Sn + Zn + M) = 0.01 〜0.5。3)如]) 中之藏鍍萆巴，其中，Sn/(Sn+Zn + M) = 0.5〜〇 8 、Zn/(Sn + Zn + M) 2·1 ～0.6, M/(Sn + Zn + M) = 0.01 ～0.5. 3) Tibetan ruthenium as in [], where Sn/(Sn+Zn + M) = 0.5~〇8,
Zn/(Sn + Zn + M)二0.25〜0.4、M/(Sn+Zn + M) = 〇.〇l〜〇·3 〇 又，本發明係提供：4)如υ〜3)中任一項之濺鍍靶， 其中，％/(211 + “）= 0.1〜〇.67。5)如1)〜3)中任一項之濺鍍 革巴，其中，Μ/(Ζη + Μ)二0.15〜〇·4。6)如1)〜5)中任一項之 濺鍍靶，其中，該3價以上之元素Μ，係擇自入卜化、Ga、Zn / (Sn + Zn + M) two 0.25 ~ 0.4, M / (Sn + Zn + M) = 〇. 〇 l ~ 〇 · 3 〇 In addition, the present invention provides: 4) such as υ ~ 3) Sputter target, wherein %/(211 + ") = 0.1~〇.67. 5) Sputtering leather according to any one of 1) to 3), wherein Μ/(Ζη + Μ) II The sputter target of any one of the above 3), wherein the elemental bismuth or higher is selected from the group consisting of Ga, Ga,
Sb中之至少一種兀素。7)如})〜6)中任一項之濺鍍靶，其 相對密度係90%以下，體電阻率係在1〇-lQcm以下。8) 一 種光資汛圯錄媒體及其製造方法，其特徵在於，係使用1)〜7) 中任一項之濺鍍靶至少作為薄膜，而形成光資訊記錄媒體 之一部份。9) 一種光資訊記錄媒體及其製造方法，其特徵 在於’係使用1)〜7)中任一項之雜萆巴至少作為薄膜，而 形成光資訊記錄媒體之一部份，且該薄膜配置成鄰接於記 錄層或反射層。 藉由將保護層材ZnS_Si〇2置換成不含硫化物僅含氧化 物之材料，可抑制因硫擴散至鄰接之反射層、記錄層等所 引起之劣化，並且能確保與ZnS_Si〇2同程度之光學特性及 非晶質安定性’且能夠高速成膜。藉此1改善光資訊記 錄媒體之特性及提昇生產性。 【貫施方式】 本發明之滅絲’其最A之特徵在於，氧化錫相（110) 之蜂值強纟II、與氧化錫以外之氧化物或複合氧化物相存 1263686 &本發明’藉由添加如此之以氧化鋅為主成分之化合物， “呆有靶之導電性’藉此，能以直流濺鍍（濺鍍 形成薄膜。 DC濺鍍與RF濺鍍相比’其因成膜速度快 '濺鍍效率 佳而較為優異。 ,又’沉@鑛之裝置廉價、控制容易，且具有耗電量 八優點。而由於保護膜本身之膜厚可薄〖，故能提昇生 產丨生並發揮基板加熱之防止效果。 本發明之濺鍍靶’如上所述，相對密度係90%以上、 體電阻率係滑Am以下，藉由使用該乾，可提高生產性、 亚付到品質優異之材料，而具能以低成本、穩定地製造且 有光碟保護膜之光記錄媒體的顯著效果。 错此’能均勻地成膜，且能形成特性優異之光資訊記 錄媒體（保護膜）。 再者，使用本發明之㈣革巴形成之薄膜，係形成光資 訊記錄媒體構造之—部份，雖配置成鄰接於記錄層或反射 層’但如上述’由於未使用ZnS，故無s造成之污染，硫 成分亦不會擴散被保護層夾狀記錄層材，藉此具有使記 錄層之劣化變無之顯著效果。 又，為了大容量化、高速記錄&，將具有高反射率、 高導熱特性之純岣或Ag合金使用於反射層材，而由於硫 成分：不會擴散至鄰接之記錄層材’巾同樣能防止反射層 材之4化腐蝕、光資訊記錄媒體之反射率等特性變差，具 有優異的效果。 又’… 1263686 具有良好之濺鍍性。 滅鍵膜之透過率，雖有隨著Sn〇2量之增加而降低之傾 向，但亦達88〜95% ( 633nm)，折射率為22〜2·4，且仍 未見特定之結晶峰，而具有安定之非晶質性（ΐ ι〜15)。 本實施例之革巴，因未使用ZnS，故不會發生因硫之擴 散、污染而導致光資訊記錄媒體之特性惡化…與後述 之比較例相比’成膜樣品之透過率、折射率、非晶質之安 定性、#巴密度、體電阻率、成膜速度皆顯示良好之值，且 能施行DC錢鍍。 比較例1-5 士表1所不’準備與本發明條件相異之原料粉成分及 組成比的材料，特別準備 一 l J 甲之ZnS，將此等以盥 貫她例相同的條件製作 ^ 成軍巴且使用该靶形成濺鍍膜。 將此結果同樣示於表1。 脫離本發明之比敎 及比較例ς 季乂例之成刀、組成，例如比較例3、 ‘乂例5 ’其體電阻座較高，故同 進行灯機鍍Μ曰㈣貫行DC⑽而 法提昇χ θ U A料度延1，而無 而為有炉、特別疋比較例5係含有多量ZnS， 巧百^ 5染危險之材料。 比較例1、1 - 1.3A/sec ,_ ，其成膜速度係分別為3.9A/SeC、 例3， ^速度慢’而無法提昇錢鑛效率。又，比較 “把讼度低、體電阻率走g過 、 比較例 /、、甩阻丰起過WOQcm以上之問題。 晶質性為 心、透過率差、體電阻率高。比較例4之非 •5 ’安定性不足。At least one halogen in Sb. 7) The sputtering target according to any one of the above items, wherein the relative density is 90% or less and the volume resistivity is 1 〇 to 1 cm or less. 8) A light-recording medium and a method of manufacturing the same, characterized in that a sputtering target according to any one of 1) to 7) is used as at least a film to form a part of an optical information recording medium. 9) An optical information recording medium and a method of manufacturing the same, characterized in that 'the use of any one of the types 1 to 7) is at least as a film to form a part of an optical information recording medium, and the film configuration Adjacent to the recording layer or the reflective layer. By replacing the protective layer material ZnS_Si〇2 with a material containing no sulfide and containing only an oxide, deterioration due to diffusion of sulfur to the adjacent reflective layer, recording layer, or the like can be suppressed, and the same degree as ZnS_Si〇2 can be ensured. The optical properties and amorphous stability are able to form a film at a high speed. In this way, the characteristics of the optical information recording medium are improved and the productivity is improved. [Cross-application method] The wire A of the present invention is characterized in that the tin-phase of the tin oxide phase (110) is strong, and the oxide or composite oxide other than tin oxide is stored. 1263686 & By adding such a compound containing zinc oxide as a main component, "targeting conductivity" can be used for DC sputtering (sputtering to form a film. DC sputtering is compared with RF sputtering) The speed is fast, the sputtering efficiency is better and better. The 'Shen@Mine's device is cheap, easy to control, and has the advantage of 8 power consumption. Because the film thickness of the protective film itself can be thin, it can improve production hygiene. In addition, as described above, the sputtering target of the present invention has a relative density of 90% or more and a volume resistivity of at least Am, and the use of the dry material improves productivity and sub-payment. The material has a remarkable effect of an optical recording medium which can be manufactured at a low cost and stably and which has a disc protective film. This is an optical information recording medium (protective film) which can form a film uniformly and has excellent characteristics. Furthermore, using the invention (4) The film formed by the bar is formed into a structure of the optical information recording medium, and is disposed adjacent to the recording layer or the reflective layer. However, as described above, since ZnS is not used, there is no pollution caused by s, and sulfur components are not diffused. The sandwiched recording layer of the protective layer has a remarkable effect of deteriorating the deterioration of the recording layer. Further, in order to increase the capacity and record high speed, a pure germanium or Ag alloy having high reflectance and high thermal conductivity is obtained. When it is used for a reflective layer material, the sulfur component does not diffuse to the adjacent recording layer material. The towel can also prevent the deterioration of the reflective layer material and the reflectance of the optical information recording medium, and has an excellent effect. Also... 1263686 has good sputtering properties. The transmittance of the bond-killing film tends to decrease with the increase of Sn〇2, but it also reaches 88~95% (633nm) and the refractive index is 22~2. ·4, and still have no specific crystallization peak, and have stable amorphous (ΐ ι 15). In this embodiment, the gram is not used because of the diffusion and contamination of sulfur. Lead to deterioration of the characteristics of optical information recording media Compared with the comparative examples described later, the transmittance of the film-forming sample, the refractive index, the stability of the amorphous state, the bar density, the volume resistivity, and the film formation rate all showed good values, and DC money plating can be performed. Example 1-5 The material of the raw material powder composition and the composition ratio which are different from the conditions of the present invention are prepared, and a ZnS is prepared in the same manner as in the case of the same example. The target was used to form a sputter film. The results are also shown in Table 1. The ratios and comparative examples of the present invention are omitted. For example, Comparative Example 3, 'Example 5' The resistor block is higher, so the lamp is plated with Μ曰 (4) through the DC (10) and the method is increased by χ θ UA. The material is extended by 1, and there is no furnace, especially the comparative example 5 contains a large amount of ZnS. Dangerous material. In Comparative Example 1, 1 - 1.3 A/sec, _, the film formation rate was 3.9 A/SeC, and Example 3, and the speed was slow, and the efficiency of the money was not improved. In addition, the problem of "lower litigation, bulk resistivity, comparative example /, and 甩 丰 过 WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO WO Non•5' stability is insufficient.