JP5510767B2 - Thin film transistor and manufacturing method thereof - Google Patents

Description

  The present invention relates to an oxide semiconductor film, a thin film transistor using the oxide semiconductor film as a channel layer, and a method for manufacturing the same.

Thin film transistors, particularly field effect transistors, are widely used as unit electronic elements, high frequency signal amplifying elements, liquid crystal driving elements and the like of semiconductor memory integrated circuits, and are currently the most widely used electronic devices.
Among them, with the remarkable development of display devices in recent years, not only liquid crystal display devices (LCD) but also various display devices such as electroluminescence display devices (EL) and field emission displays (FED) are used as display elements. Thin film transistors (TFTs) are frequently used as switching elements that drive a display device by applying a driving voltage.
In addition, silicon semiconductor compounds are most widely used as the material. Generally, silicon single crystals are used for high-frequency amplifying elements and integrated circuit elements that require high-speed operation. Amorphous silicon is used because of the demand for large area.
However, a crystalline silicon-based thin film needs a high temperature of, for example, 800 ° C. or higher when crystallizing, and is difficult to construct on a glass substrate or an organic substrate. For this reason, there is a problem that it can be formed only on an expensive substrate having high heat resistance such as a silicon wafer or quartz, and a lot of energy and the number of steps are required for manufacturing.
In addition, the crystalline silicon-based thin film is usually difficult to reduce the cost by reducing the number of masks because the element structure of the TFT is limited to the top gate structure.
On the other hand, an amorphous silicon semiconductor (amorphous silicon) that can be formed at a relatively low temperature has a lower switching speed than a crystalline one, so that when used as a switching element for driving a display device, a high-speed moving image The display may not be followed.
Furthermore, there is a problem that the characteristics as a switching element are deteriorated, for example, when the semiconductor layer is irradiated with visible light, the semiconductor layer exhibits conductivity and a leakage current is generated, which may cause malfunction. Therefore, a method of providing a light shielding layer that blocks visible light is known. For example, a metal thin film is used as the light shielding layer.
However, providing a light shielding layer made of a metal thin film not only increases the number of processes, but also has a floating potential, so the light shielding layer needs to be at the ground level, and in such a case, parasitic capacitance is generated. is there.
Currently, as a switching element for driving a display device, an element using a silicon-based semiconductor layer occupies the mainstream, but it has a switching speed in addition to the stability and workability of the silicon-based thin film. This is because various performances such as high speed are good. Such silicon-based thin films are generally manufactured by a chemical vapor deposition (CVD) method.
Further, a conventional thin film transistor (TFT) has a gate electrode, a gate insulating layer, a semiconductor layer such as hydrogenated amorphous silicon (a-Si: H), a source and a drain electrode on a substrate such as glass. There is a stacked inverted stagger structure, and it is used as a drive element for flat panel displays and the like represented by active matrix liquid crystal displays in the field of large area devices including image sensors. In these applications, even those using amorphous silicon have been required to operate at higher speeds with higher functionality.
Under these circumstances, in recent years, an oxide semiconductor thin film using a metal oxide has attracted attention as a material for a semiconductor layer, as it is more stable than a silicon-based thin film.

However, among oxide semiconductor thin films made of such metal oxides, in particular, an oxide semiconductor thin film formed by crystallizing zinc oxide at a high temperature is transparent, but has a field effect mobility of 1 cm ² / V · sec. The on / off ratio is small. Moreover, since leakage current is likely to occur, it has been difficult to put it to practical use industrially. In addition, many studies have been made on crystalline oxide semiconductor thin films using zinc oxide, but the following problems occur when films are formed by sputtering, which is commonly used in industry. was there.
That is, the TFT performance may be lowered, such as low field-effect mobility, low on / off ratio, large leakage current, unclear pinch-off, and normally on. In addition, since the chemical resistance is inferior, there are limitations on the manufacturing process and the use environment such that wet etching is difficult. Furthermore, in order to improve the performance, it is necessary to form a film at a high pressure, which slows the film formation rate, and there is a problem in industrialization such as a high temperature treatment of 700 ° C. or higher. In addition, TFT performance such as electrolytic mobility in the bottom gate configuration is low, and there is a limitation on the TFT device configuration, such as the need for a film thickness of 50 nm or more in the top gate configuration to improve performance (Patent Document 1). ).
In order to solve such a problem, a method of preparing an amorphous oxide semiconductor thin film made of indium oxide and zinc oxide and driving a thin film transistor has been studied (Patent Document 2). However, an amorphous oxide semiconductor thin film made of indium oxide and zinc oxide has a problem in that an off current is high and it is difficult to obtain an on / off ratio in a transistor.
On the other hand, since complex oxides of indium, zinc and gallium have been conventionally studied as transparent conductive films, specific studies have hardly been made (Patent Document 3).
However, when an oxide semiconductor thin film made of indium oxide, gallium oxide, and zinc oxide is used as a thin film transistor, in order to keep the S value small or to reduce the threshold shift due to stress, a corresponding thermal history (for example, 350 It was necessary to apply a heat treatment at a high temperature of 1 ° C. or more for 1 hour or more. In addition, there is a problem that it is easily affected by surroundings such as light and air (Non-Patent Document 1).

JP 2003-86808 A US Patent Publication No. 2005/0199959 JP 2000-44236 A Kim, Chang Jung et al. Highly Stable Ga2O3-In2O3-ZnO TFT for Active-Matrix Organic Light-Emitting Diode Display Application, Electron Devices Meeting, 2006. IEDM '06. International (ISBN: 1-4244-0439-8)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thin film transistor having a high on / off ratio and a small off current, and a method for manufacturing the same.
The present invention also provides a liquid crystal display and an organic EL display using the thin film transistor.

The present invention has found that a thin film transistor having a high on-off ratio and a low off-current can be provided by doping a specific amount of specific atoms into an oxide semiconductor layer included in a thin film transistor. The present invention specifically includes:
1. A thin film transistor including an oxide semiconductor layer, wherein the oxide semiconductor layer contains 5 × 10 ²⁰ to 5 × 10 atoms selected from the group consisting of nitrogen atoms, helium atoms, neon atoms, argon atoms, and mixtures thereof. ^{The present} invention relates to a thin film transistor including an atomic concentration of ²¹ atoms / cm ³ .
2. 2. The thin film transistor according to 1 above, wherein the oxide semiconductor layer is composed of an oxide containing at least In (indium) and Zn (zinc) in the following atomic ratio.
In / X = 0.200-0.600
Zn / X = 0.400-0.800
(Where X is the number of all metal atoms other than oxygen contained in the oxide)
3. 2. The thin film transistor according to 1 above, wherein the oxide semiconductor layer is composed of an oxide containing at least In (indium) and Zn (zinc) in the following atomic ratio.
In / X = 0.920-0.999
Zn / X = 0.080-0.001
(Where X is the number of all metal atoms other than oxygen contained in the oxide)
4). It includes a step of forming an oxide film by DC or AC sputtering of an oxide sputtering target, and a step of heat-treating the oxide film at 70 to 500 ° C. to form an oxide semiconductor layer. It is related with the manufacturing method of the thin-film transistor of any one of said 1-3.
5. It is related with the liquid crystal display containing the thin-film transistor of any one of said 1-3.
6). It is related with an organic electroluminescent display containing the thin-film transistor of any one of said 1-3.

According to the present invention, a thin film transistor having a low off-state current, particularly a field effect transistor, can be obtained with good reproducibility.

(1) Oxide semiconductor layer Oxide semiconductor layer of the present invention
(1-1) Atomic concentration of doped atom The oxide semiconductor layer of the present invention has an atom selected from the group consisting of a nitrogen atom, a helium atom, a neon atom, an argon atom, and a mixture thereof (wherein the atom is represented by “ Called "doped atoms"). By introducing such doped atoms into the oxide semiconductor layer, the reliability of the semiconductor can be improved. The reason why the group consisting of a nitrogen atom, a helium atom, a neon atom, an argon atom, and a mixture thereof is preferable is that an effect of not reacting with the oxide contained in the oxide semiconductor layer occurs, and thus the oxide semiconductor layer is This is because an off current of the thin film transistor used is increased and an on / off ratio is improved.
The atomic concentration of doped atoms in the oxide semiconductor layer is, for example, 5 × 10 ^{20 to} 5 × 10 ²¹ atoms / cm ³ , preferably 6 × 10 ²⁰ to 4 × 10 ²¹ atoms / cm ³ , more preferably 7 × 10. ^{A value of 20 to} 3 × 10 ²¹ atoms / cm ³ is appropriate.
The atomic concentration of the doped atoms can be measured and quantified by, for example, a secondary ion mass spectrometer (SIMS).

The doped atoms are doped in the oxide semiconductor layer. In order to control the doping atom to a predetermined concentration, the doping atom (N _{2 in} the case of nitrogen) is 80 to 100% by volume, preferably 85 to 100% by volume, more preferably 90 to 100% by volume. (For example, 100 to 800 ° C., preferably 200 to 500 ° C.) for a predetermined time (for example, 1 minute to 100 hours, preferably 30 minutes to 10 hours) or ions of the doped atoms themselves There is a way to inject. In the case where the oxide semiconductor layer is formed by sputtering, nitrogen, helium, argon, or the like can be simultaneously introduced into an atmosphere of oxygen or argon for sputtering.

(1-2) Contained Element The oxide semiconductor layer includes an oxide containing not only the above-described doped atoms but also at least indium (In) and zinc (Zn) in a predetermined ratio. Examples of the third additive metal element (M) other than indium (In) and zinc (Zn) contained in the oxide include gallium (Ga).

The atomic ratio of each element of indium (In) and zinc (Zn) contained in the oxide containing indium (In) and zinc (Zn) at a predetermined ratio is, for example,
In / X = 0.200-0.600, Zn / X = 0.400-0.800
Preferably,
In / X = 0.250-0.550, Zn / X = 0.450-0.550
Particularly preferably,
In / X = 0.300-0.500, Zn / X = 0.500-0.700
It is. Here, X is the number of all metal atoms other than oxygen contained in the oxide.
When indium (In) and zinc (Zn) are within the above range, the oxide semiconductor layer of the present invention has a stable amorphous structure and operational stability is improved.

Another preferable range of the atomic ratio of each element of indium (In) and zinc (Zn) contained in the oxide containing indium (In) and zinc (Zn) in a predetermined ratio is In / X = 0.920 to 0.999 Zn / X = 0.001 to 0.080
Preferably,
In / X = 0.940-0.990, Zn / X = 0.010-0.060
Particularly preferably,
In / X = 0.950-0.980, Zn / X = 0.020-0.050
It is. Here, X is the number of all metal atoms other than oxygen contained in the oxide.
If indium (In) and zinc (Zn) are within this range, the semiconductor layer has a stable crystal structure by heating, so that reliability is improved.

(1-3) Physical properties / Thickness of oxide semiconductor layer The thickness of the oxide semiconductor layer is, for example, 1 to 100 nm, preferably 10 to 90 nm, and more preferably 50 to 80 nm. is there.
-Surface roughness of oxide semiconductor layer The surface roughness (RMS) of the semiconductor film is preferably 0.5 nm or less, more preferably 0.3 nm or less, and particularly preferably 0.2 to 0.1 nm.

(2) Thin Film Transistor The thin film transistor of the present invention includes a substrate, a semiconductor layer, a protective layer for the semiconductor layer, a source electrode, a drain electrode, a gate insulating film, and a gate electrode.
(2-1) Substrate Examples of the substrate include a glass substrate, an organic substrate, a silicon substrate (silicon wafer, quartz), and the like. Examples of the organic substrate include polymer materials such as polycarbonate resin, polyarylate resin, polyester resin such as polyethylene terephthalate and polyethylene naphthalate, polyether sulfone resin, amorphous polyolefin resin, polystyrene resin, and acrylic resin. In view of availability, a glass substrate is preferable.

(2-2) Oxide Semiconductor Layer The oxide semiconductor layer of the present invention refers to a region where carriers are induced by the electric field effect, and is preferably defined as a region within 10 nm from the interface in contact with the insulating film. . The semiconductor layer functions as a switching element because its resistance is changed by the induction of carriers.

(2-3) Protective layer of oxide semiconductor layer The protective layer is a layer intended to prevent the influence of the operating atmosphere in the oxide semiconductor layer of the present invention. The protective layer can be used in the bottom gate type structure shown in FIG. If the bottom gate type thin film transistor is not provided with a protective layer, the main part of the semiconductor layer is exposed, so that the effect of the protective layer is great. Note that in the top-gate thin film transistor, the substrate serves as a protective layer (FIG. 3).
A material for forming the protective layer of the oxide semiconductor layer is not particularly limited as long as the material can protect the oxide semiconductor layer from the ambient atmosphere, particularly oxygen and water. What is generally used can be arbitrarily selected as long as the effects of the invention of the present embodiment are not lost. For _{example, SiO 2, SiNx, Al 2} O 3, Ta 2 O 5, TiO 2, MgO, ZrO 2, CeO 2, K 2 O, Li 2 O, Na 2 O, Rb 2 O, Sc 2 O 3, Y Oxides such as ₂ O ₃ , Hf ₂ O ₃ , CaHfO ₃ , PbTi ₃ , BaTa ₂ O ₆ , SrTiO ₃ , and AlN can be used. Among _{these, SiO 2, SiNx, Al 2} O 3, Y 2 O 3, Hf 2 O 3, it is preferable to use CaHfO _3, more preferably _{SiO 2, SiNx, Y 2 O} 3, Hf 2 O 3 , CaHfO ₃ , particularly preferably oxides such as SiO ₂ , Y ₂ O ₃ , Hf ₂ O ₃ , and CaHfO ₃ . The number of oxygen in these oxides does not necessarily match the stoichiometric ratio (for example, it may be SiO ₂ or SiOx).
Such a protective layer may have a structure in which two or more different insulating films are stacked. As the insulating film, the same composition and the material forming the protective film, i.e. _{SiO 2, SiNx, Al 2 O} 3, Ta 2 O 5, TiO 2, MgO, ZrO 2, CeO 2, K 2 O, Li ₂ O, Na ₂ O, Rb ₂ O, Sc ₂ O ₃ , Y ₂ O ₃ , Hf ₂ O ₃ , CaHfO ₃ , PbTi ₃ , BaTa ₂ O ₆ , SrTiO ₃ , and AlN.
The protective layer may be crystalline, polycrystalline, or amorphous, but is preferably polycrystalline or amorphous that is easy to produce industrially. It is particularly preferable that the protective layer is amorphous.

(2-4) Electrode The thin film transistor of the present invention includes three types of electrodes: a drain electrode, a source electrode, and a gate electrode.
There are no particular limitations on the material for forming the gate electrode, the source electrode, and the drain electrode, and any material generally used can be selected as long as the effects of the present embodiment are not lost. For example, transparent electrodes such as indium tin oxide (ITO), indium zinc oxide, ZnO, SnO ₂ , metal electrodes such as Al, Ag, Cr, Ni, Mo, Au, Ti, Ta, Cu, or these An alloy metal electrode can be used. Moreover, it is preferable to laminate two or more layers to reduce the contact resistance or improve the interface strength. In order to reduce the contact resistance of the source electrode and the drain electrode, the resistance of the interface with the semiconductor electrode may be adjusted by plasma treatment, ozone treatment, or the like.
An alloy may be used as a material for the source and drain electrodes. By using an alloy as a material for these electrodes, the durability and adhesion of the electrodes can be enhanced. Examples of the material constituting the alloy include a copper-manganese alloy (Cu-Mn) and an alloy containing copper such as Cu-Ni; an alloy containing Al such as Al-Nd, Al-Ce, and Al-Ni; Examples thereof include alloys containing Ag and Cu such as Ag—Pd—Cu and Ag—Au—Cu. When an alloy layer containing copper or the like is combined with a semiconductor layer with low resistance and high mobility, a large-screen high-definition display can be realized. There is no limitation on an alloy containing copper, but a copper-manganese alloy (Cu-Mn) is preferable because of its low resistance and less problems of peeling and surface oxidation. Further, Al, Ag, Cu or the above Cu alloy, Al alloy, or Ag alloy may be sandwiched with a metal such as Ti or Mo.

(2-5) Gate Insulating Film The material for forming the gate insulating film is not particularly limited as long as it can insulate between the oxide semiconductor layer (channel layer) of the present invention and the gate electrode. What is generally used can be arbitrarily selected as long as the effects of the invention of the present embodiment are not lost. For _{example, SiO 2, SiNx, Al 2} O 3, Ta 2 O 5, TiO 2, MgO, ZrO 2, CeO 2, K 2 O, Li 2 O, Na 2 O, Rb 2 O, Sc 2 O 3, Y Oxides such as ₂ O ₃ , Hf ₂ O ₃ , CaHfO ₃ , PbTi ₃ , BaTa ₂ O ₆ , SrTiO ₃ , and AlN can be used. Among _{these, SiO 2, SiNx, Al 2} O 3, Y 2 O 3, Hf 2 O 3, it is preferable to use CaHfO _3, more preferably _{SiO 2, SiNx, Y 2 O} 3, Hf 2 O 3 , CaHfO ₃ , particularly preferably oxides such as SiO ₂ , Y ₂ O ₃ , Hf ₂ O ₃ , and CaHfO ₃ . The number of oxygen in these oxides does not necessarily match the stoichiometric ratio (for example, it may be SiO ₂ or SiOx).
Such a gate insulating film may have a structure in which two or more different insulating films are stacked. The insulating film may be the same composition as the material forming the protective film. When stacked, the side in contact with the semiconductor is preferably an oxide film such as SiO ₂ . The gate insulating film may be crystalline, polycrystalline, or amorphous, but is preferably polycrystalline or amorphous that is easy to manufacture industrially. An amorphous film having a flat interface is particularly preferable.

(2-6) Other Layers The thin film transistor of the present invention can further include other layers such as a contact layer.
The contact layer is disposed at each interface between the semiconductor layer and the source electrode and between the semiconductor layer and the drain electrode, and has a function of reducing a carrier injection barrier. Examples of the material constituting the contact layer include high carrier concentration transparent oxides such as ITO and IZO. Although there is no particular limitation on the method for forming the contact layer, a layer having a composition or composition ratio different from that of the oxide semiconductor layer of the present invention is formed, or the contact portion with the semiconductor electrode is increased in resistance by plasma treatment or ozone treatment. Alternatively, when the semiconductor layer is formed, a layer whose resistance is increased by a film formation condition such as oxygen partial pressure may be used as the contact layer.

(2-7) Properties of Thin Film Transistor The ratio W / L of TFT channel width W to channel length L is usually 0.1 to 100, preferably 1 to 20, and particularly preferably 2 to 8 (see FIG. 2). .
The distance between the source electrode and the drain electrode (channel length L) is, for example, 0.5 to 50 μm, preferably 1 to 30 μm, and more preferably 2 to 20 μm. The channel width W is, for example, 1-100 μm, preferably 5-50 μm, and more preferably 10-30 μm.
On-off ratio The on-off ratio is the current flowing between the source electrode and the drain electrode when a predetermined voltage is applied between the source electrode and the drain electrode and the gate voltage is changed from -30 V to 30 V, for example. This value is obtained by dividing the maximum value by the minimum value. The on / off ratio is preferably 10 ⁶ or more, more preferably 10 ⁷ or more, and particularly preferably 10 ⁸ or more.

(3) Manufacturing method of thin film transistor The thin film transistor of the present invention comprises:
(A) a step of forming an oxide film by DC or AC sputtering of an oxide sputtering target, and (B) a step of heat-treating the oxide film at 70 to 500 ° C. to form an oxide semiconductor layer,
Manufactured by.

(A) Process-Preparation of Sputtering Target An oxide film is formed by DC or AC sputtering of an oxide sputtering target.
The oxide sputtering target is manufactured, for example, as follows.
(A) Raw material preparation step First, a mixed oxide of indium oxide and zinc oxide is prepared. The average particle diameter of the mixed oxide is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm when the granulation process described later is not performed. When the granulation process described later is performed, if the average particle size of the mixed oxide is in the range of 0.01 to 10 μm, the particles can be prevented from agglomerating, further improving the mixing property and obtaining a dense sintered body. This is preferable.
In obtaining the above mixed oxide, indium and zinc oxides, chlorides, inorganic acid salts, hydroxides and the like excluding oxygen can be used as raw materials. The purity of each raw material is preferably 99% or more, more preferably 99.9% or more, and particularly preferably 99.99% or more. If the purity of the raw material is 99% or more, it is preferable because a dense oxide sintered body having a desired volume resistivity can be obtained.
When an oxide is used as the raw material for each component, a predetermined amount of each oxide (raw material) powder is placed in a mixer such as a ball mill, jet mill, pearl mill or the like so as to obtain a target having the desired composition. The desired mixed oxide can be obtained by pulverizing and mixing them. At this time, the pulverization / mixing time is preferably 1 to 100 hours, more preferably 5 to 50 hours, and particularly preferably 10 to 50 hours. 1 to 100 hours is preferable because mixing is sufficient and economical. There is no particular restriction on the temperature during pulverization / mixing, but room temperature (25 ° C.) is preferred.

  When a material other than an oxide is used as a raw material for each component, a predetermined amount of the raw material is put into a mixer such as a ball mill, jet mill, pearl mill or the like so as to obtain a target having a desired composition. After pulverizing and mixing to obtain a mixture, the mixture is calcined, and the obtained calcined product is pulverized by the mixer or the like to obtain a target mixed oxide. The calcining temperature and calcining time at this time are preferably approximately 800 to 1600 ° C. and 1 to 100 hours, though depending on the type of raw material. If it is 800 degreeC or more or 1 hour or more, since thermal decomposition of a raw material becomes enough, it is preferable. Furthermore, if it is 1600 degrees C or less or 100 hours or less, there is no possibility that a raw material will sinter and a particle coarsening will occur. More preferable calcination temperature and calcination time are 1000 to 1300 ° C. and 2 to 50 hours.

The calcination / pulverization process described above may be performed once, or the operation of further calcination / pulverization may be performed as many times as desired for the mixed oxide obtained by pulverizing the calcined product. Moreover, you may obtain the target mixed oxide by performing the calcination and the grinding | pulverization process mentioned above using the oxide as a raw material of each component.
The calcining temperature and calcining time in the case where the object of calcining is a mixed oxide once obtained or an oxide as a raw material are also approximately 800 to 1600 ° C. and preferably 1 to 100 hours. If it is 800 degreeC or more or 1 hour or more, since thermal decomposition of a raw material will become enough, it is preferable if it is 1600 degrees C or less or 100 hours or less, without the possibility that a raw material may sinter and particle coarsening will occur. . More preferable calcination temperature and calcination time are 1000 to 1300 ° C. and 2 to 50 hours.
Moreover, the target mixed oxide can be prepared also by granulating the mixed oxide obtained as mentioned above, or granulating the raw material of each component. This granulation can be performed by a conventional method such as a spray drying method. When granulation is performed by a spray drying method, a solution obtained by adding a binder such as polyvinyl alcohol to an aqueous solution or an alcohol solution of the mixed oxide or raw material is used. The granulation conditions vary depending on the solution concentration and the added amount of the binder, but are adjusted so that the average particle size of the granulated product is 1 to 100 μm, preferably 5 to 100 μm, particularly preferably 10 to 100 μm. Here, the average particle diameter refers to an average particle diameter measured by a microscope method in which the particle size distribution is measured by measuring the size and number of particles on a microscope image. By performing this granulation, it is possible to improve the fluidity and filling property during molding. If the average particle diameter of the granulated product is 100 μm or less, it is preferable because the fluidity and filling property during molding are good and the effect of granulation is obtained.

(B) Forming step In this step, the mixed oxide obtained in the raw material preparation step is formed into a desired shape prior to sintering. Molding can be performed by mold molding, casting molding, injection molding, pressure molding, etc., but CIP (cold isostatic pressure) and HIP (hot isostatic pressure) are necessary to obtain a sintered body with a high relative density. It is preferable to perform pressure molding by such a method. The shape of the molded body can be various shapes suitable as a target. Further, polyvinyl alcohol, methyl cellulose, polywax, oleic acid or the like may be used as a molding aid. The molding pressure is preferably 10 kg / cm ^{2 to} 100 t / cm ² , more preferably 100 kg / cm ^{2 to} 100 t / cm ² . The molding time is preferably 10 minutes to 10 hours. A molding pressure of 10 kg / cm ² or more, or a molding time of 10 minutes or more is preferable because a sintered body having a high relative density can be obtained.

(C) Sintering step In this step, the molded product obtained in the molding step is sintered to obtain an oxide sintered body. As a sintering method, HIP sintering, hot press sintering, normal pressure sintering, etc. can be applied, but normal pressure sintering is preferable from the viewpoint of economy. As for sintering temperature, 1200-1600 degreeC is preferable, More preferably, it is 1250-1550 degreeC, More preferably, it is 1300-1500 degreeC. If it is 1200 degreeC or more, since the oxide sintered compact which has sufficient relative density can be obtained, and the oxide sintering which has the target volume resistivity can be obtained even if it anneals later, it is preferable. . Moreover, if it is 1600 degrees C or less, the shift | offset | difference of a composition will not arise. Although depending on the sintering temperature, the sintering time is preferably 1 to 50 hours, more preferably 2 to 30 hours, and particularly preferably 3 to 20 hours. If it is 1 hour or more, sintering is sufficiently performed, and if it is 50 hours or less, it is economical because it is economical. The atmosphere during sintering is air or a reducing atmosphere. Examples of the reducing atmosphere include reducing gas atmospheres such as H ₂ , methane, and CO, and inert gas atmospheres such as Ar and N ₂ .

(D) Target evaluation In order to obtain a target that is less susceptible to abnormal discharge or cracking during sputtering, the impurity concentration, density, and electrical resistance of the obtained oxide sintered body (sputtering target) are important. It is measured and managed as follows.
(i) Impurity concentration The concentration of impurities is measured by ICP (Inductively Coupled Plasma Atomic Emission Analysis) on the target piece after sintering. The impurity concentration is preferably 500 ppm or less, but this is not the case when a sintering aid selected from Group 3 metals, Group 4 metals, and rare earths is added for the purpose of increasing density and decreasing electrical resistance.
(ii) Density The density of the target is measured by the Archimedes method. In order to prevent abnormal discharge, the density is preferably 5 g / cm 3 or more.
(iii) The electrical resistance of the electrical resistance target can be measured using a Loresta manufactured by Mitsubishi Holding Corporation. The specific resistance of the target is preferably 5 mΩ · cm or less in order to stably perform DC sputtering advantageous in terms of productivity and equipment cost.

Sputtering Examples of the sputtering method include AC sputtering, RF sputtering, and DC sputtering.
Compared with RF sputtering, DC sputtering reduces damage during film formation. When used as a thin film transistor, threshold voltage (Vth) decreases, threshold voltage shift (ΔVth) decreases, carrier mobility improves, Effects such as a decrease in S value can be expected.
Here, the threshold voltage (Vth) refers to a voltage when the drain current rises when a gate voltage (drain voltage) is applied. The threshold voltage (Vth) shift refers to a change in Vth that occurs when a gate voltage (drain voltage) is applied. If the Vth shift is small, it can be said that the operation as a semiconductor is stable. The shift amount of the threshold voltage (Vth) is, for example, 0.01 to 5.0 V, preferably 0.05 to 2.0 V, more preferably 0.1 to 1.0 V.
Here, the S value (Swing Factor) is a value indicating the steepness of the drain current that rapidly rises from the off state to the on state when the gate voltage is increased from the off state. As defined by the following equation, an increment of the gate voltage when the drain current increases by one digit (10 times) is defined as an S value.
S value = dVg / dlog (Ids)
The smaller the S value, the sharper the rise ("All about Thin Film Transistor Technology", Ikuhiro Ukai, 2007, Industrial Research Committee). When the S value is large, it is necessary to apply a high gate voltage when switching from on to off, and power consumption may increase.
In addition, when AC sputtering is used, since nodules of the target do not grow, generation of particles during film formation can be suppressed, and an improvement in yield can be expected.

Sputtering conditions In order to obtain an oxide semiconductor layer with uniform carrier mobility, there are methods such as heating the substrate during sputtering, heat treatment after forming the oxide semiconductor layer, or laser heating. In order to obtain a carrier mobility of 100 cm ² / Vs or higher, it is preferable that heating be performed after the wet process after forming the oxide semiconductor layer as described above. For example, in the case of a top contact element, (1) semiconductor layer film formation, (2) source / drain electrode film formation, (3) source / drain electrode patterning are processed in this order, but (3) patterning process If the semiconductor layer is immersed in a chemical solution, the semiconductor layer heating step is preferably performed at least after the chemical solution is immersed.

The moisture pressure when forming the oxide semiconductor layer of the present invention is preferably 10 ⁻³ Pa or less, more preferably 10 ⁻⁴ Pa or less, and further preferably 10 ⁻⁵ Pa or less. preferable. The moisture pressure can be quantified by, for example, a quadrupole mass spectrometer.

Step (B) Further, the oxide film obtained in step (A) is heat-treated at 70 to 500 ° C., preferably 100 to 400 ° C., more preferably 200 to 350 ° C. to form an oxide semiconductor layer. The heat treatment time depends on the above temperature, but is, for example, 10 minutes to 50 hours, more preferably 30 minutes to 20 hours, and still more preferably 40 minutes to 10 hours. The heat treatment is performed, for example, by a method using a known electric furnace or clean oven.

(4) Applications The thin film transistor of the present invention is included in liquid crystal displays and organic EL displays. Preferably, it is used as a member for a liquid crystal drive driver of a liquid crystal display or as a member for a light emission control driver of an organic EL display.
Examples of the present invention will be described below, but the present invention is not limited to the embodiments of the following examples.

(1) Production of sputtering target [Target I]
As raw materials, powders of indium oxide and zinc oxide were mixed so that the atomic ratio [In / (In + Zn)] was 0.20 and the atomic ratio [Zn / (In + Zn)] was 0.80. This was supplied to a wet ball mill and mixed and ground for 72 hours to obtain a raw material fine powder.
After granulating the obtained raw material fine powder, it is press-molded to a size of 10 cm in diameter and 5 mm in thickness, put in a firing furnace, fired under conditions of 1,500 ° C. for 12 hours, and sintered body (Target I) was obtained.
The target I was pulverized and analyzed by inductively coupled plasma emission spectrometry (manufactured by SII, model number SPS5100). As a result, Sn (tin), Ge (germanium), Si (silicon), Ti (titanium), Zr (zirconium), Hf ( Hafnium) and other impurities were not included. Moreover, the bulk resistance of the target I was 30 mΩ, and the relative density was 0.96.

[Target II]
As the target I, except that indium oxide and zinc oxide powder were mixed as raw materials so that the atomic ratio [In / (In + Zn)] was 0.99 and the atomic ratio [Zn / (In + Zn)] was 0.01. A raw material fine powder was obtained, granulated, molded, and fired to obtain a sintered body (target II).
When target II was pulverized and analyzed by ICP, impurities such as Sn (tin), Ge (germanium), Si (silicon), Ti (titanium), Zr (zirconium), and Hf (hafnium) were not contained. Moreover, the bulk resistance of the target II was 8 mΩ, and the relative density was 0.97.

(2) Measurement of atomic ratio of sputtering target In order to measure the atomic ratio of doped atoms contained in the sputtering targets I and II obtained in (1) above, an oxide semiconductor layer was formed as follows. The ratio was measured.
The sputtering targets I and II obtained in (1) above are mounted on a DC magnetron sputtering film forming apparatus, which is one of the DC sputtering methods, and an oxide semiconductor layer is formed on a glass substrate (Corning 1737). did.
As sputtering conditions here, substrate temperature: 25 ° C., ultimate pressure: 1 × 10 ⁻⁶ Pa, atmospheric gas: Ar 99% and oxygen 1.0%, sputtering pressure (total pressure): 2 × 10 ⁻¹ Pa, The input power was 100 W, the film formation time was 8 minutes, and the ST distance was 100 mm.
Before film formation of the oxide semiconductor layer, the chamber is sufficiently baked (80 ° C.), the ultimate pressure is sufficiently lowered (10 ⁻⁴ Pa or less), and the substrate is loaded using a load lock. Reduced water pressure. When H ₂ O (water) in the sputtering chamber was analyzed with a quadrupole mass spectrometer (Q-mass, manufactured by Nippon Vacuum Co., Ltd., model number MSQ-100) and the water pressure during film formation was measured, 1 × 10 ^{− 5} Pa or less.
As a result, an oxide semiconductor layer having a thickness of 70 nm was formed on the glass substrate.
Note that when the composition of the obtained oxide semiconductor layer was analyzed by an ICP method, the atomic ratio [In / X] of the target I was 0.21 and the atomic ratio [Zn / X] was 0.79. In the target II, the atomic ratio [In / X] was 0.99, and the atomic ratio [Zn / X] was 0.01. Here, X is the number of all metal atoms other than oxygen contained in the oxide.

(3) Fabrication of thin film transistor [Example 1]
-Gate electrode After depositing 200 nm of Mo gate metal on a silicon substrate with a thermal oxide film by RF sputtering at room temperature, patterning was performed by wet etching to produce a gate electrode on the substrate.
Gate insulating film Silicon nitride (SiNx) was laminated by PECVD at 300 ° C. to obtain a gate insulating film.
-Oxide semiconductor layer Using target I, the oxide semiconductor layer was formed into a film by sputtering. Sputtering was performed under the same conditions as in (2), and an oxide film was formed on the gate insulating film and then patterned.
Source electrode and drain electrode By using a lift-off process and RF magnetron sputtering (room temperature, Ar 100%), a source electrode, a drain electrode and a gate electrode obtained by simultaneously forming a source electrode and a drain electrode made of In ₂ O ₃ —ZnO are used. The ratio W / L of the configured channel width W and channel length L (FIG. 2) was 4 (W = 20 μm, L = 5 μm).
-Doping atom doping Further, the obtained oxide semiconductor layer was heat-treated in 100% nitrogen at 300 ° C for 1 hour (corresponding to the step (B)), and nitrogen was doped into the oxide semiconductor layer ( Nitrogen annealing).
Protective layer finally SiO ₂ protective layer (passivation film) was formed (Fig. 1). In this way, a bottom gate, top contact type thin film transistor was obtained.

[Examples 2 to 19]
Thin film transistors of Examples 2 to 19 were obtained in the same manner as in Example 1 except that the composition of metal atoms contained in the oxide semiconductor layer and the annealing time of nitrogen annealing (step (B)) were different.
[Example 20]
A thin film transistor of Example 20 was obtained in the same manner as Example 15 except that an ion implantation method was used instead of nitrogen annealing as a doping method of the doped atoms. Here, in the ion implantation method, ion implantation of nitrogen atoms was performed using an ion implantation apparatus (model number IMX-3500RS, manufactured by Nippon Vacuum Engineering Co., Ltd.) under the conditions of an output of 20 KeV and a dose of 10 ¹⁵ cm ⁻² .

[Example 21]
When the oxide semiconductor layer was formed by sputtering, the atmosphere during sputtering was set to Ar: N ₂ : O ₂ = 80: 19: 1, and nitrogen annealing and ion implantation were not performed. Thus, a thin film transistor was obtained.
[Example 22]
A thin film transistor was obtained in the same manner as in Example 20 except that in doping of the doped atoms, annealing was performed in an Ar 100% atmosphere instead of a nitrogen atmosphere, the annealing temperature was 500 ° C., and the annealing time was 1 hour.
[Example 23]
A thin film transistor was obtained in the same manner as in Example 20 except that annealing was performed in an Ar 100% atmosphere instead of a nitrogen atmosphere in the doping of the doping atoms, the annealing temperature was 300 ° C., and the annealing time was 1 hour.
[Comparative Examples 1 to 10]
Thin film transistors of Comparative Examples 1 to 10 were obtained in the same manner as in Example 1 except that the composition of metal atoms contained in the oxide semiconductor layer, the atmosphere gas for annealing, and the annealing time were changed as shown in Table 2. In addition, Comparative Examples 9 and 10 are [Example 24] with respect to Examples 16 and 17, respectively.
A thin film transistor was obtained in the same manner as in Example 3 except that Corning 1373 was used for the substrate.

(4) Evaluation / Dope Atom Concentration The depth direction distribution of the nitrogen concentration in the semiconductor film of the transistor obtained in Example 1 was measured using SIMS.
As a result, it was found that the average nitrogen concentration in the vicinity of the insulating film interface (40 to 50 nm) was 5.0 × 10 ²¹ cm ⁻³ .
・ On-off ratio and threshold voltage shift amount Using a semiconductor parameter analyzer (Keutley 4200), the thin film transistors of each example and comparative example were measured at room temperature (25 ° C.), in vacuum (1 × 10 ⁻³ Pa), and in a light-shielding environment. The on / off ratio and the threshold voltage shift amount (ΔVth) were obtained.
The on / off ratio is a value obtained by applying 3 V between the source and drain, changing the gate voltage from −30 V to 30 V in 1 V increments, and dividing the maximum value of the current flowing between the source and drain by the minimum value. .
The threshold voltage shift amount (ΔVth) is applied as a stress condition with a gate voltage of 15 V and a DC voltage of 10 μA at 50 ° C. for 100 hours, and the threshold voltage (Vth) before and after the stress is compared to compare the threshold voltage shift amount (ΔVth). Asked.
In addition, the stability of a thin film transistor is generally evaluated in four stages based on μc-Si: ◎: very good as a semiconductor device, ○: excellent, △: normal, ×: unusable. Judged.

1 is a schematic diagram of a bottom-gate thin film transistor. FIG. 2 is a schematic diagram illustrating a measurement part of a channel width W and a channel length L of the thin film transistor of FIG. 1. 1 is a schematic view of a top-gate thin film transistor.

Explanation of symbols

1 Board
2 Gate electrode
3 Gate insulation film
4 Semiconductor layer
5 Source electrode
6 Drain electrode
7 Protective layer

Claims (5)

A thin film transistor including an oxide semiconductor layer, the oxide semiconductor layer, a nitrogen atom, helium atom, neon atoms, argon atoms and atoms of 5 × 10 ²⁰ ~5 × 10 is selected from the group consisting of mixtures A thin film transistor including an atomic concentration of ²¹ atoms / cm ³ , wherein the oxide semiconductor layer includes an oxide containing at least In (indium) and Zn (zinc) in the following atomic ratio.
In / X = 0.200-0.600
Zn / X = 0.400-0.800
(Where X is the number of all metal atoms other than oxygen contained in the oxide) A thin film transistor including an oxide semiconductor layer, the oxide semiconductor layer, a nitrogen atom, helium atom, neon atoms, argon atoms and atoms of 5 × 10 ²⁰ ~5 × 10 is selected from the group consisting of mixtures A thin film transistor including an atomic concentration of ²¹ atoms / cm ³ , wherein the oxide semiconductor layer includes an oxide containing at least In (indium) and Zn (zinc) in the following atomic ratio.
In / X = 0.920-0.999
Zn / X = 0.080-0.001
(Where X is the number of all metal atoms other than oxygen contained in the oxide) It includes a step of forming an oxide film by DC or AC sputtering of an oxide sputtering target, and a step of heat-treating the oxide film at 70 to 500 ° C. to form an oxide semiconductor layer. method of manufacturing a thin film transistor according to claim 1 or 2. To claim 1 or 2 including a thin film transistor according, a liquid crystal display. To claim 1 or 2 including a thin film transistor according an organic EL display.

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