WO2015029272A1 - Sintered body and amorphous film - Google Patents

Abstract

The present invention addresses the problem of providing a sintered body that makes it possible to obtain a transparent conductive film that is capable of maintaining suitable transmittance of visible light and conductivity, particularly an amorphous film having a low refractive index. This thin film has high transmittance and excellent mechanical properties, and is therefore useful for transparent conductive films for displays and protective films for optical devices. The purpose of the present invention is to use the thin film to improve the properties of optical devices, reduce equipment costs, and greatly improve film formation properties.

Description

Sintered body and amorphous film

The present invention relates to a sintered body capable of obtaining a transparent conductive film having good visible light transmittance and conductivity, and an amorphous film having a low refractive index and produced using the sintered body.

Conventionally, as a transparent conductive film, a film in which tin is added to indium oxide, that is, an ITO (Indium-Tin-oxide) film is transparent and excellent in electrical conductivity, and is used in a wide range of applications such as various displays. However, this ITO has a problem that the manufacturing cost is inferior because indium which is a main component is expensive.

For this reason, for example, a proposal using a film using zinc oxide (ZnO) as an alternative to ITO has been made. Since the film is mainly composed of zinc oxide, there is an advantage that the price is low. Such a film is known to increase in conductivity due to oxygen vacancies in ZnO, which is the main component, and if the film properties of conductivity and light transmission are similar to those of ITO, the use of such materials will increase. there's a possibility that.

By the way, when using visible light in a display or the like, the material needs to be transparent, and it is particularly preferable that the material has a high transmittance in the entire visible light region. In addition, if the refractive index is high, the optical loss increases and the viewing angle dependency of the display deteriorates. Therefore, the refractive index is low, and the film is an amorphous film to improve the film cracking and etching performance. It is also desirable.

Since the amorphous film has low stress, cracks are unlikely to occur compared to the crystalline film, and it is considered that the amorphous film will be required for display applications toward flexible use. The above ITO needs to be crystallized in order to improve the resistance value and transmittance, and if it is amorphous, it absorbs in the short wavelength region and does not become a transparent film. Not suitable for.

As materials using zinc oxide, IZO (indium oxide-zinc oxide), GZO (gallium oxide-zinc oxide), AZO (aluminum oxide-zinc oxide) and the like are known (Patent Documents 1 to 3). However, although IZO can be a low-resistance amorphous film, it has a problem that it has absorption in a short wavelength region and has a high refractive index. Further, GZO and AZO are likely to become crystallized films due to the ease of ZnO c-axis orientation, and such crystallized films have problems such as film peeling and film cracking because stress increases.

In addition, Patent Document 4 discloses a light-transmitting conductive material that realizes a wide range of refractive index, mainly composed of ZnO and an alkaline earth metal fluoride compound. However, this is a crystallized film, and the effect of the amorphous film as in the present invention described later cannot be obtained. Patent Document 5 discloses a transparent conductive film that has a low refractive index and a low specific resistance and is amorphous. However, the composition system differs from the present invention, and the refractive index and the resistance value are disclosed. Cannot be adjusted together.

JP 2007-008780 A JP 2009-184876 A JP 2007-238375 A Japanese Patent Laid-Open No. 2005-219982 JP 2007-035342 A

An object of the present invention is to provide a transparent conductive film capable of maintaining good visible light transmittance and conductivity, in particular, a sintered body capable of obtaining an amorphous film having a low refractive index. Since this thin film has high transmittance and excellent mechanical properties, it is useful as a transparent conductive film for displays and a protective film for optical disks. Accordingly, it is an object to improve the characteristics of the optical device, reduce the equipment cost, and greatly improve the film forming characteristics.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, by replacing the conventional transparent conductive film such as ITO with the material system shown below, the resistivity and the refractive index can be arbitrarily set. It is possible to adjust to the above, ensuring optical characteristics equal to or higher than those of conventional ones, enabling stable film formation by sputtering or ion plating, and providing the thin film by forming an amorphous film. We obtained knowledge that the characteristics and productivity of optical devices can be improved.

Based on this finding, the present invention provides the following inventions.
1) An oxide sintered body composed of zinc (Zn), first metal element (M1), second metal element (M2), germanium (Ge) and / or silicon (Si), and oxygen (O). M1 is one or more elements selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), yttrium (Y) and indium (In) (provided that the second metal When the element is yttrium, yttrium is removed from the first metal element group, and when the second metal element is indium, indium is removed from the first metal element group.), M2 is yttrium ( Y), indium (In), manganese (Mn), lanthanum (La), scandium (Sc), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), One or more elements selected from the group consisting of rubium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), lutetium (Lu), promethium (Pm), and M1 Amol% total content in terms of oxide of, Bmol% in total content of oxides in terms of M2, when the total content of Ge and / or Si is that the C mol% with GeO ₂ and / or SiO ₂ in terms of, A sintered body characterized by satisfying the condition of 15 ≦ A + B + C ≦ 55.
2) The total content of the first metal element (M1) and the second metal element (M2) is 10 at% or more in terms of the atomic number ratio of (M1 + M2) / (Zn + M1 + M2) Sintered body.
3) The above item 2, wherein the total content of the first metal element (M1) and the second metal element (M2) is 15 at% or more in terms of the atomic ratio of (M1 + M2) / (Zn + M1 + M2). Sintered body.
4) The sintered body according to 1 above, wherein the total content of Ge and / or Si is 5 ≦ C ≦ 30.
5) The sintered body according to any one of 1 to 4 above, further comprising 0.1 to 5 wt% of a metal that forms an oxide having a melting point of 1000 ° C. or less in terms of oxide weight.
6) An oxide having a melting point of 1000 ° C. or lower is B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O _3. 6. The sintered body according to 5 above, which is one or more oxides selected from the group consisting of MoO ₃ .
7) The sintered body according to any one of 1 to 6 above, wherein the relative density is 90% or more.
8) The sintered body according to any one of 1 to 7 above, wherein the bulk resistance value is 10 Ω · cm or less.

9) A sputtering target using the sintered body described in any one of 1 to 8 above.
10) An ion plating material using the sintered body described in any one of 1 to 8 above.

11) An oxide sintered body composed of zinc (Zn), first metal element (M1), second metal element (M2), germanium (Ge) and / or silicon (Si), and oxygen (O). M1 is one or more elements selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), yttrium (Y) and indium (In) (provided that the second metal When the element is yttrium, yttrium is removed from the first metal element group, and when the second metal element is indium, indium is removed from the first metal element group.), M2 is yttrium ( Y), indium (In), manganese (Mn), lanthanum (La), scandium (Sc), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd) One or more elements selected from the group consisting of terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), lutetium (Lu), promethium (Pm), and M1 Amol% total content in terms of oxide of, Bmol% in total content of oxides in terms of M2, when the total content of Ge and / or Si is that the C mol% with GeO ₂ and / or SiO ₂ in terms of, A thin film that satisfies the condition of 15 ≦ A + B + C ≦ 55 and is amorphous.
12) The above-mentioned item 11, wherein the total content of the first metal element (M1) and the second metal element (M2) is such that the atomic number ratio of (M1 + M2) / (Zn + M1 + M2) is 10 at% or more. Thin film.
13) The total content of the first metal element (M1) and the second metal element (M2) is such that the atomic ratio of (M1 + M2) / (Zn + M1 + M2) is 15 at% or more. Thin film.
14) The thin film as described in any one of 11 to 13 above, wherein the total content of Ge and / or Si is 5 ≦ C ≦ 30.
15) The thin film as described in any one of 11 to 14 above, further comprising 0.1 to 5 wt% of a metal forming an oxide having a melting point of 1000 ° C. or less in terms of oxide weight.
16) An oxide having a melting point of 1000 ° C. or lower is B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O _3. 16. The thin film as described in 15 above, which is one or more oxides selected from the group consisting of MoO ₃ .
17) The thin film as described in any one of 11 to 16 above, which has an extinction coefficient of 0.01 or less at a wavelength of 450 nm.
18) The thin film as described in any one of 11 to 16 above, which has a refractive index of 2.00 or less at a wavelength of 550 nm.
19) The thin film as described in any one of 11 to 16 above, which has a volume resistivity of 1 × 10 ⁻³ to 1 × 10 ⁹ Ω · cm.

20) The method for producing a sintered body according to any one of 1 to 8 above, wherein the raw material powder is mixed, and the obtained mixed powder is 900 ° C to 1500 ° C under an inert gas or vacuum atmosphere. The sintered product is characterized in that it is pressure-sintered by pressurization or press-molding the obtained mixed powder, and then the compact is sintered at 900 ° C. to 1500 ° C. under an inert gas or vacuum atmosphere. A method for producing a knot.

Replacing a conventional transparent conductive film such as ITO with the materials shown above, it becomes possible to arbitrarily adjust the resistivity and refractive index, ensuring optical characteristics equal to or higher than those of the conventional, and sputtering. Alternatively, stable film formation by ion plating is possible, and further, by using an amorphous film, there is an excellent effect that it becomes possible to improve the characteristics and productivity of an optical device including the film. .

It is a figure which shows the X-ray-diffraction spectrum of Example 1 and Comparative Example 1 of this invention.

The present invention relates to an oxide comprising zinc (Zn), a first metal element (M1), a second metal element (M2), germanium (Ge) and / or silicon (Si), and oxygen (O) as constituent elements. a sintered body, Amol%, Bmol%, Ge and / or the total content of Si is GeO ₂ and / or SiO ₂ are in terms of oxide total content of M2 in the total content of oxides in terms of M1 When converted to Cmol%, the condition of 15 ≦ A + B + C ≦ 55 is satisfied.

Said 1st metal element (M1) is a trivalent metal element, Comprising: From the group which consists of aluminum (Al), gallium (Ga), boron (B), yttrium (Y), and indium (In). One or more elements selected. However, when the second metal element described later is yttrium, yttrium is excluded from the group of the first metal elements, and when the second metal element is indium, the first metal element Indium is removed from the group.

The second metal element (M2) is a rare earth metal element that forms a Bigsbite structure (rare earth oxide C type) when formed into an oxide, and includes yttrium (Y), indium (In), and manganese. (Mn), lanthanum (La), scandium (Sc), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium It is one or more elements selected from the group consisting of (Er), ytterbium (Yb), lutetium (Lu), and promethium (Pm).

In the present invention, when adjusting the raw materials, the balance is adjusted so that the balance of each oxide is 100 mol% with the balance being ZnO, and therefore the Zn content is obtained from the ZnO conversion of such balance. be able to. By setting it as such a composition, the amorphous film of a low refractive index can be formed and the said effect of this invention is acquired.
In the present invention, the content of each metal in the sintered body is specified in terms of oxides. This is because some or all of the metals in the sintered body exist as complex oxides. In addition, in the component analysis of a sintered body that is usually used, each content is measured not as an oxide but as a metal.

Germanium oxide (GeO ₂ ) and silicon dioxide (SiO ₂ ) contained in the sintered body of the present invention are vitrification components (glass-forming oxides), and are effective components for amorphizing (vitrifying) the film. It is. On the other hand, this vitrification component reacts with zinc oxide (ZnO) to form a substance such as ZnGe ₂ O ₄ , which may become a partially crystalline film. The film has a large film stress and may cause film peeling or film cracking.
In order to crystallize such a film, the applicant of the present invention has previously proposed a trivalent metal element (first metal as referred to in the present invention) in Japanese Patent Application No. 2013-119611 (filing date: June 6, 2013). Element) to form a mullite composition (3M ₂ O ₃ -2GeO ₂ , 3M ₂ O ₃ -2SiO ₂ : M is a trivalent metal element), and the generation of a substance that causes such crystallization. Proposed means to inhibit.

However, the addition of such a trivalent metal element was effective in inhibiting the formation of a substance that causes crystallization, but it is sufficient that crystallization occurs at a place unrelated to the formation of such a substance. In some cases, it could not be suppressed. For this reason, as a result of further intensive studies, the inventors of the present application have conducted research on the second metal element (which forms a Big Sbite structure (rare earth oxide C type) together with the first metal element when formed into an oxide). It has been found that the addition of a rare earth metal element can promote the amorphization. This is because, by adding an oxide having a rare earth oxide C type to a material system mainly composed of ZnO having a hexagonal wurtzite type crystal structure, the crystal structure is distorted and inhibits crystallization. This is probably due to this.

The oxides of the first metal element, the oxide of the second metal element, and the glass-forming oxides such as germanium oxide and silicon dioxide described above are lower refractive materials than zinc oxide (ZnO). By adding this oxide, the refractive index of the film can be lowered. On the other hand, when the composition is adjusted so as to lower the refractive index (when ZnO is reduced), the resistance value tends to increase. Therefore, the total addition amount of the oxide of the first metal element is Amol%, the total addition amount of the oxide of the second metal element is Bmol%, and the total addition amount of germanium oxide and / or silicon dioxide is Cmol%. In this case, 15 ≦ A + B + C ≦ 55.
When A + B + C is less than 15 mol%, the above-described crystallization suppression effect cannot be obtained, and the film is difficult to become amorphous. On the other hand, when A + B + C exceeds 70 mol%, the content of ZnO decreases. Since it becomes an insulating film, it is not preferable.

The first metal element and the second metal element contribute to conductivity as a dopant for zinc oxide (ZnO). Since Al, Ga, B, Y, and In which are the first metal elements have a low refractive index, adjustment of the refractive index and the resistance value can be facilitated by a combination with the glass-forming oxide. Oxides composed of these metal elements can be added individually and in combination, respectively, and the object of the present invention can be achieved. Of the second metal elements effective for amorphization, In and Y are preferable because they have a small increase in resistance value, and In is particularly preferable because Y has a smaller increase in resistance value than Y.
In addition, since the present invention is characterized in that both the first metal element and the second metal element are added, when In is selected as the second metal element, from the group of the first metal elements It should be understood that when In is removed and Y is selected as the second metal element, Y is removed from the group of first metal elements.

In the present invention, as described above, the contents of the first metal element and the second metal element are defined in terms of oxides, but the oxide here is M when the metal element is M, It means an oxide composed of M ₂ O ₃ . For example, when the first metal element is aluminum (Al), it means an oxide made of Al ₂ O _3, and when the second metal element is yttrium (Y), it means an oxide made of Y ₂ O _3. To do.

In the present invention, the total content of the first metal element (M1) and the second metal element (M2) is preferably 10 at% or more in terms of the atomic number ratio of (M1 + M2) / (Zn + M1 + M2). Is at least 15 at%. In this case, it is effective for lowering the refractive index and making it amorphous. In order to exert this effect, the atomic ratio is 10 at% or more, more preferably 15 at% or more.
In the present invention, the total content of Ge and / or Si constituting the glass-forming oxide is preferably 5 mol% or more and 30 mol% or less in terms of GeO ₂ and / or SiO ₂ . If the amount is less than 5 mol%, the effect of lowering the refractive index becomes small and the effect of sufficient amorphization cannot be obtained. If it exceeds 30 mol%, the bulk resistance value of the sintered body tends to increase, and stable DC sputtering can be achieved. Because it becomes difficult.

Furthermore, the sintered body of the present invention comprises a metal that forms an oxide (low melting point oxide) having a melting point of 1000 ° C. or lower as a basic material (zinc oxide, oxide of the first metal element, oxidation of the second metal element). Product, glass-forming oxide) in an amount of 0.1 to 5 wt% in terms of oxide weight.
Since zinc oxide (ZnO) is easy to reduce and evaporate, the sintering temperature cannot be increased so much, and it may be difficult to improve the density of the sintered body. However, the addition of such a low-melting point oxide has an effect that a high density can be achieved without increasing the sintering temperature so much. If it is less than 0.1 wt%, the effect cannot be exhibited, and if it exceeds 5 wt%, the characteristics may be changed.

Examples of the low melting point oxide include B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , MoO. ₃ can be mentioned. These oxides can be added individually and in combination, respectively, and the object of the present invention can be achieved. Note that the low-melting-point oxide becomes a liquid phase at the time of sintering and acts as a sintering aid, so that the sintering temperature can be lowered. The above-mentioned effect is difficult to obtain because the melting point is increased by becoming a product or by dissolving in a solid solution. Therefore, it is preferable not to synthesize after adding the low melting point oxide.
The sintered body of the present invention can be used as a sputtering target. In that case, the relative density is preferably 90% or more. The improvement in density has the effect of increasing the uniformity of the sputtered film and suppressing the generation of particles during sputtering.

焼 結 The sintered body of the present invention can achieve a relative density of 90% or more and a bulk resistance of 10 Ω · cm or less. By increasing the density of the sintered body, it is possible to provide a sputtering target with less generation of particles. Further, by reducing the bulk resistance value, high-speed film formation by direct current (DC) sputtering becomes possible. Depending on the selection of the material, radio frequency (RF) sputtering or magnetron sputtering is required, but even in that case, the deposition rate is improved. By improving the deposition rate, production throughput can be improved, which can greatly contribute to cost reduction.

The sintered body of the present invention can also be used as an ion plating material. This is because by appropriately selecting the constituent elements and the composition ratio, the vapor pressure or the like is lowered, and ion plating becomes possible.
The ion plating method is a technique in which a metal is evaporated in a vacuum with an electron beam, ionized by high-frequency plasma, etc. (cations), and a negative potential is applied to the substrate to accelerate and attach the cations to form a film. It is. Ion plating has the advantages of higher material use efficiency and higher productivity than sputtering.
When used as an ion plating material, a plate-like product obtained by finishing the sintered body can be used, or a powder or granular material obtained by further pulverizing the sintered body can be used. A powder or granulated product is more preferable from the viewpoint of production efficiency because it is more easily evaporated than a plate-like product.

In the present invention, it is important that the film obtained by sputtering the target obtained by processing the sintered body or the film formed by the ion plating is amorphous (amorphous film). . Whether or not the obtained film is an amorphous film can be determined by observing the diffraction intensity around 2θ = 34.4 ° where the peak of the (002) plane of ZnO appears using, for example, an X-ray diffraction method. . A thin film containing ZnO as a main component has a large film stress. Therefore, if it is a crystallized film, cracks and cracks occur, and further problems such as film peeling occurred. However, this thin film should be an amorphous film. Therefore, it is possible to avoid problems such as cracks and cracks due to film stress.

A film formed by sputtering a target obtained by machining the sintered body of the present invention or a film formed by the above ion plating can achieve an extinction coefficient of 0.01 or less at a wavelength of 450 nm. it can. A thin film for display needs to be transparent in the entire visible light range, but an oxide-based film such as an IZO film generally has absorption in a short wavelength region, so that it is difficult to develop a clear blue color. It was. According to the present invention, since the extinction coefficient at a wavelength of 450 nm is 0.01 or less and there is almost no absorption in a short wavelength region, it can be said that the material is extremely suitable as a transparent material.

Further, the film formed by sputtering the target obtained by machining the sintered body of the present invention or the film formed by the ion plating has a refractive index at a wavelength of 550 nm of 2.00 or less (preferably, 1.90 or less) can be achieved. Furthermore, the volume resistivity of the film can be 1 × 10 ⁻³ to 1 × 10 ⁹ Ω · cm.
As described above, the oxide composed of the first metal element, the second metal element, germanium oxide (GeO ₂ ), and silicon dioxide (SiO ₂ ) is a material having a lower refractive index than zinc oxide (ZnO). Therefore, a film having a refractive index lower than that of the conventional film can be obtained by adding these oxides.

Further, a film formed by sputtering a target obtained by machining the sintered body of the present invention, or a film formed by the above ion plating is an optical adjustment film or a transparent conductive film in various displays, Moreover, it can use for the optical thin film which forms the protective layer of an optical information recording medium. In the case of the protective layer of the optical information recording medium, since ZnS is not used, there is a remarkable effect that there is no contamination due to S and no deterioration of the recording layer due to this.

Hereinafter, description will be made based on examples and comparative examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.

Measurement methods, measurement conditions, and the like in Examples and Comparative Examples are as follows.
(About component composition)
Measuring apparatus: SPS3500DD manufactured by SII
Measuring method: ICP-OES (High Frequency Inductively Coupled Plasma Atomic Emission Analysis)
(About relative density)
The density of the sintered body was calculated from the weight measurement by determining the volume of the sintered body by length measurement.
The theoretical density was obtained by multiplying each single element density of the raw material oxide by the mixing mass ratio and totaling the obtained values. The relative density was obtained by dividing the density of the oxide sintered body by the theoretical density and multiplying by 100.
Theoretical density = Σ (oxide density × mixing mass ratio)
Relative density = {(density of sintered body) / (theoretical density)} × 100
(Bulk resistance, specific resistance, sheet resistance)
Measuring device: NPS resistivity meter Σ-5 +
Measurement method: DC four-point probe method (refractive index, extinction coefficient)
Measuring device: Spectrophotometer UV-2450 manufactured by SHIMADZU
Measurement method: Calculated from transmittance and front / back surface reflectance (deposition method and conditions)
Deposition system: ANELVA SPL-500
Substrate: φ4inch
Substrate temperature: Room temperature (about crystallization evaluation)
Measuring device: Rigaku X-ray diffraction device Ultimate IV
Tube: Cu
Tube voltage: 40 kV
Tube current: 30 kV

Example 1
After mixing and synthesizing a basic material (base material) composed of ZnO powder, Ga ₂ O ₃ powder, In ₂ O ₃ powder, and SiO ₂ powder at a blending ratio (mol%) shown in Table 1, low melting point oxide B ₂ O ₃ powder was added at a blending ratio (wt%) described in Table 1 with respect to the base material and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 99.9% and the bulk resistance was 1.4 mΩ · cm.

Further, sputtering was performed using the finished target. The sputtering conditions, DC sputtering, sputtering power of 500 W, O ₂ (oxygen) and Ar gas pressure 0.5Pa containing 0 ~ 2 vol%, was formed to a thickness of 1500 ~ 7000 Å. At this time, stable sputtering was possible. The amorphousness (amorphous), refractive index (wavelength 550 nm), volume resistivity, and extinction coefficient (wavelength 450 nm) of the film formation sample were measured. As shown in FIG. 1, the thin film formed by sputtering is an amorphous film. As shown in Table 1, the refractive index is 1.87 (wavelength 550 nm) and the extinction coefficient is less than 0.01 (wavelength 450 nm). An amorphous film having a low refractive index was obtained. The volume resistivity changed depending on the amount of oxygen in the sputtering atmosphere, and exceeded 5 × 10 ⁰ Ω · cm.

As described above, the amorphous film was evaluated when the peak attributed to the ZnO (002) plane was not clearly recognized by the X-ray diffraction method. Specifically, the peak intensity I ₁ attributed to the ZnO (002) plane is I ₁ / I ₀ ≦ 5. 2 with respect to the intensity I ₀ (background) in the 2θ range where no peak attributed to the constituent composition exists. When 0 was satisfied, it was evaluated as an amorphous film (corresponding to ○ in Table 1), and when I ₁ / I ₀ > 5.0 was satisfied, it was evaluated as a crystallized film (corresponding to x in Table 1). For example, in Example 1, the maximum peak value at 30 ° <2θ <35 ° in FIG. 1 is the ZnO (002) peak intensity I ₁ , while no peaks attributed to constituent components are observed on both sides of the ZnO peak. The average value of peak intensities at 27 ° <2θ <30 ° and 40 ° <2θ <43 ° was I _0, and I ₁ / I ₀ was calculated. As a result, I ₁ / I ₀ = 1.6 in Example 1, and I ₁ / I ₀ = 37.3 in Comparative Example 1 described later, which were evaluated as an amorphous film and a crystallized film, respectively.

(Example 2)
After mixing and synthesizing a basic material (base material) composed of ZnO powder, Al ₂ O ₃ powder, In ₂ O ₃ powder, and SiO ₂ powder at a blending ratio (mol%) shown in Table 1, low melting point oxide B ₂ O ₃ powder was added at a blending ratio (wt%) described in Table 1 with respect to the base material and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 100.4%, and the bulk resistance was 3.0 mΩ · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.85 (wavelength 550 nm), the volume resistivity is more than 6 × 10 ⁶ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

Example 3
After mixing and synthesizing a basic material (base material) composed of ZnO powder, Ga ₂ O ₃ powder, Y ₂ O ₃ powder, and SiO ₂ powder at a blending ratio (mol%) shown in Table 1, low melting point oxide B ₂ O ₃ powder was added at a blending ratio (wt%) described in Table 1 with respect to the base material and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 100.6% and the bulk resistance was 1.2 mΩ · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.87 (wavelength 550 nm), the volume resistivity is more than 1 × 10 ⁸ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

Example 4
ZnO powder, _Ga 2 _{O 3} powder, _{an In} 2 _{O 3} powder, was blended with the base material of SiO ₂ powder blending ratio of (matrix) are described in Table 1 (mol%), B as a low-melting-point oxide ₂ O ₃ powder was added to the base material at a blending ratio (wt%) described in Table 1 and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 99.9% and the bulk resistance was 1.4 mΩ · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.89 (wavelength 550 nm), the volume resistivity is more than 5 × 10 ⁰ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

(Example 5)
After mixing and synthesizing a basic material (base material) composed of ZnO powder, B ₂ O ₃ powder, In ₂ O ₃ powder, and GeO ₂ powder at a mixing ratio (mol%) shown in Table 1, low melting point oxide Bi ₂ O ₃ powder was added at a blending ratio (wt%) described in Table 1 with respect to the base material and mixed. Next, this mixed powder was press-molded at a pressure of 500 kgf / cm ² , and the compact was sintered under normal pressure at a temperature of 1200 ° C. in a vacuum. Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 97.6%, and the bulk resistance became 1.7 Ω · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.89 (wavelength 550 nm), the volume resistivity is more than 3 × 10 ⁶ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

(Example 6)
After mixing and synthesizing a basic material (base material) composed of ZnO powder, Ga ₂ O ₃ powder, In ₂ O ₃ powder, GeO ₂ powder at a blending ratio (mol%) shown in Table 1, low melting point oxide B ₂ O ₃ powder was added at a blending ratio (wt%) described in Table 1 with respect to the base material and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 99.7% and the bulk resistance was 1.3 mΩ · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.82 (wavelength 550 nm), the volume resistivity is more than 3 × 10 ⁻³ Ω · cm, and the extinction coefficient is 0. An amorphous film having a low refractive index of less than 01 (wavelength 450 nm) was obtained.

(Example 7)
ZnO powder, _Ga 2 _{O 3} powder, _{an In} 2 _{O 3} powder, was blended base material made of SiO ₂ powder (the base material) in the compounding ratio described in Table 1 (mol%), it was mixed thereto. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1150 ° C. and a pressure of 250 kgf / cm ² . No low melting point oxide was added. Thereafter, this sintered body was finished into a sputtering target shape by machining. As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density reached 98.2%, and the bulk resistance became 1.1 mΩ · cm.

Further, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. The coefficient (wavelength 450 nm) was measured. At this time, stable DC sputtering was possible. As shown in Table 1, the thin film formed by sputtering is an amorphous film, the refractive index is 1.88 (wavelength 550 nm), the volume resistivity is more than 3 Ω · cm, and the extinction coefficient is less than 0.01 (wavelength 450 nm). ) And a low refractive index amorphous film was obtained.

(Comparative Example 1)
ZnO powder, after compounding _Ga 2 _{O 3} powder, basic material consisting of GeO ₂ powder (the base material) in the compounding ratio described in Table 1 (mol%), were mixed thereto. The second metal element was not added. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining.

As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density was 96.2% and the bulk resistance was 1.2 mΩ · cm. However, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. As a result of measuring the coefficient (wavelength 450 nm), as shown in FIG. 1, the thin film formed by sputtering was not an amorphous film. The refractive index was 1.95 (wavelength 550 nm), the volume resistivity was more than 4 × 10 ⁻³ Ω · cm, and the extinction coefficient was less than 0.01 (wavelength 450 nm).

(Comparative Example 2)
A basic material (base material) composed of ZnO powder, Al ₂ O ₃ powder, Y ₂ O ₃ powder, and SiO ₂ powder was mixed and synthesized at a blending ratio (mol%) of A + B + C> 55 as shown in Table 1. Thereafter, B ₂ O ₃ powder as a low melting point oxide was added to the base material at a blending ratio (wt%) described in Table 1 and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1100 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining.

As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density was 97.4%, the bulk resistance was 36 kΩ · cm, and the resistance value was remarkably increased. Sputtering was performed using the above-finished target under the same conditions as in Example 1. However, since DC sputtering could not be performed, a film was formed by RF sputtering. As a result of measuring the amorphousness (amorphous), refractive index (wavelength 550 nm), volume resistivity, and extinction coefficient (wavelength 450 nm) of the film formation sample, as shown in Table 1, the volume resistance of the thin film formed by sputtering is shown. The rate was over 1 × 10 ⁹ Ω · cm, indicating insulation. The amorphous film had a refractive index of 1.88 (wavelength 550 nm) and an extinction coefficient of less than 0.01 (wavelength 450 nm).

(Comparative Example 3)
A basic material (base material) composed of ZnO powder, Al ₂ O ₃ powder, Y ₂ O ₃ powder, and SiO ₂ powder was mixed and synthesized at a blending ratio (mol%) of A + B + C <15 as shown in Table 1. Thereafter, B ₂ O ₃ powder as a low melting point oxide was added to the base material at a blending ratio (wt%) described in Table 1 and mixed. Next, this mixed powder was hot press sintered in an argon atmosphere under the conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, this sintered body was finished into a sputtering target shape by machining.

As a result of measuring the bulk resistance and relative density of the obtained target, as shown in Table 1, the relative density was 99.6% and the bulk resistance was 3.2 mΩ · cm. However, sputtering was performed under the same conditions as in Example 1 using the finished target, and the film formation sample was amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, extinction. As a result of measuring the coefficient (wavelength 450 nm), as shown in FIG. 1, the thin film formed by sputtering was not an amorphous film. The refractive index was 1.95 (wavelength 550 nm), the volume resistivity was more than 4 × 10 ⁻³ Ω · cm, and the extinction coefficient was less than 0.01 (wavelength 450 nm).

The sintered body of the present invention can be used as a sputtering target or an ion plating material, and a thin film formed using these sputtering target or ion plating material can protect a transparent conductive film and an optical disk in various displays. Forming a film has an effect of having extremely excellent characteristics in terms of transmittance, refractive index, and conductivity. In addition, the main feature of the present invention is that it is an amorphous film, and therefore has an excellent effect that the cracking and etching performance of the film can be remarkably improved.

In addition, since the sputtering target using the sintered body of the present invention has a low bulk resistance value and a relative density of 90% or higher, stable DC sputtering is possible. And there is a remarkable effect that the controllability of sputtering, which is a feature of this DC sputtering, can be facilitated, the film forming speed can be increased, and the sputtering efficiency can be improved. RF sputtering is performed as necessary, but even in this case, the film formation rate is improved. In addition, particles (dust generation) and nodules generated during sputtering during film formation can be reduced, and quality variation can be reduced and mass productivity can be improved.

Furthermore, since the ion plating material using the sintered body of the present invention can form an amorphous film having a low refractive index, it is possible to suppress the occurrence of cracks and cracks due to film stress, and film peeling. It has the effect. Such an amorphous film is particularly useful as an optical thin film for forming a protective layer of an optical information recording medium, an optical adjustment film in various displays, or a transparent electrode thin film.

Claims (20)

1. An oxide sintered body composed of zinc (Zn), first metal element (M1), second metal element (M2), germanium (Ge) and / or silicon (Si), oxygen (O), M1 is one or more elements selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), yttrium (Y), and indium (In) (provided that the second metal element is yttrium) In this case, yttrium is excluded from the first metal element group, and indium is excluded from the first metal element group when the second metal element is indium.), M2 is yttrium (Y), indium (In), manganese (Mn), lanthanum (La), scandium (Sc), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium ( b) one or more elements selected from the group consisting of dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), lutetium (Lu), and promethium (Pm), When the content is Amol% in terms of oxide, the total content of M2 is Bmol% in terms of oxide, and the total content of Ge and / or Si is Cmol% in terms of GeO ₂ and / or SiO ₂ , 15 ≦ A sintered body characterized by satisfying the condition of A + B + C ≦ 55.
2. The total content of the first metal element (M1) and the second metal element (M2) is 10 at% or more in terms of the atomic ratio of (M1 + M2) / (Zn + M1 + M2). Sintered body.
3. The total content of the first metal element (M1) and the second metal element (M2) is 15 at% or more in terms of the atomic ratio of (M1 + M2) / (Zn + M1 + M2). Sintered body.
4. 2. The sintered body according to claim 1, wherein the total content of Ge and / or Si is 5 ≦ C ≦ 30.
5. 5. The sintered body according to claim 1, further comprising 0.1 to 5 wt% of a metal that forms an oxide having a melting point of 1000 ° C. or less in terms of oxide weight.
6. The oxide having a melting point of 1000 ° C. or lower is B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , The sintered body according to claim 5, wherein the sintered body is one or more oxides selected from the group consisting of MoO ₃ .
7. The sintered body according to any one of claims 1 to 6, wherein the relative density is 90% or more.
8. The sintered body according to any one of claims 1 to 7, wherein a bulk resistance value is 10 Ω · cm or less.
9. A sputtering target comprising the sintered body according to any one of claims 1 to 8.
10. An ion plating material using the sintered body according to any one of claims 1 to 8.
11. An oxide sintered body composed of zinc (Zn), first metal element (M1), second metal element (M2), germanium (Ge) and / or silicon (Si), oxygen (O), M1 is one or more elements selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), yttrium (Y), and indium (In) (provided that the second metal element is yttrium) In this case, yttrium is excluded from the first metal element group, and indium is excluded from the first metal element group when the second metal element is indium.), M2 is yttrium (Y), indium (In), manganese (Mn), lanthanum (La), scandium (Sc), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (T b), one or more elements selected from the group consisting of dysprosium (Dy), holmium (Ho), erbium (Er), ytterbium (Yb), lutetium (Lu), and promethium (Pm), When the content is Amol% in terms of oxide, the total content of M2 is Bmol% in terms of oxide, and the total content of Ge and / or Si is Cmol% in terms of GeO ₂ and / or SiO ₂ , 15 ≦ A thin film that satisfies the condition of A + B + C ≦ 55 and is amorphous.
12. The total content of the first metal element (M1) and the second metal element (M2) is 10 at% or more in terms of the atomic ratio of (M1 + M2) / (Zn + M1 + M2). Thin film.
13. The total content of the first metal element (M1) and the second metal element (M2) is 15 at% or more in terms of the atomic ratio of (M1 + M2) / (Zn + M1 + M2). Thin film.
14. 14. The thin film according to claim 11, wherein the total content of Ge and / or Si is 5 ≦ C ≦ 30.
15. 15. The thin film according to claim 11, further comprising 0.1 to 5 wt% of a metal that forms an oxide having a melting point of 1000 ° C. or less in terms of oxide weight.
16. The oxide having a melting point of 1000 ° C. or lower is B ₂ O ₃ , P ₂ O ₅ , K ₂ O, V ₂ O ₅ , Sb ₂ O ₃ , TeO ₂ , Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , The thin film according to claim 15, wherein the thin film is one or more oxides selected from the group consisting of MoO ₃ .
17. The thin film according to any one of claims 11 to 16, wherein an extinction coefficient at a long wavelength of 450 nm is 0.01 or less.
18. The thin film according to any one of claims 11 to 16, wherein the refractive index at a long wavelength of 550 nm is 2.00 or less.
19. Thin film according to any one of claims 11 to 16, wherein the volume resistivity is ^{1 × 10 -3 ~ 1 × 10} 9 Ω · cm.
20. The method for producing a sintered body according to any one of claims 1 to 8, wherein raw material powder is mixed, and the obtained mixed powder is 900 ° C to 1500 ° C under an inert gas or vacuum atmosphere. The sintered product is characterized in that it is pressure-sintered by pressurization or press-molding the obtained mixed powder, and then the compact is sintered at 900 ° C. to 1500 ° C. under an inert gas or vacuum atmosphere. A method for producing a knot

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