TWI631579B - Sintered body and amorphous film - Google Patents

Sintered body and amorphous film Download PDF

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TWI631579B
TWI631579B TW102120877A TW102120877A TWI631579B TW I631579 B TWI631579 B TW I631579B TW 102120877 A TW102120877 A TW 102120877A TW 102120877 A TW102120877 A TW 102120877A TW I631579 B TWI631579 B TW I631579B
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film
sintered body
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powder
oxide
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TW102120877A
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TW201405580A (en
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奈良淳史
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Jx日鑛日石金屬股份有限公司
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Abstract

The present invention is a sintered body characterized by comprising zinc (Zn), a trivalent metal element, germanium (Ge) and/or germanium (Si), and oxygen (O), and the total content of the trivalent metal element is When the oxide content is set to A mol%, the total content of Ge and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , 15 A+B

Description

Sintered body and amorphous film

The present invention relates to a sintered body which can obtain a transparent conductive film having good visible light transmittance and conductivity, and an amorphous film having a low refractive index produced by 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 indium of the main component is expensive, and thus it is inferior in manufacturing cost.

For the above reasons, for example, a proposal has been made to use a film using zinc oxide (ZnO) as a substitute for ITO. Since it is a film containing zinc oxide as a main component, it has the advantage of being inexpensive. Such a film is known to have an increase in conductivity due to oxygen vacancies of the main component ZnO, and if the film properties of conductivity and light transmittance are similar to those of ITO, there is a possibility that the use of such a material is increased.

In other words, when visible light is used in a display or the like, the material must be transparent, and it is particularly preferable to have high transmittance in the entire visible light region. Further, if the refractive index is high, the optical loss is increased, or the viewing angle dependence of the display is deteriorated. Therefore, it is desirable that the refractive index is low, or an amorphous film is desired in order to improve the cracking or etching performance of the film.

Since the amorphous film has a small stress, it is less likely to be cracked than the crystalline film. An amorphous film will be required for future display applications that are moving toward flexibility. Further, conventional ITO must be crystallized in order to increase the electric resistance value or transmittance, and if it is formed into an amorphous state, it has absorption in a short-wavelength region and cannot be a transparent film, and thus is not suitable for such use.

As a material 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 form a low-resistance amorphous film, it has a problem of absorption in a short-wavelength region and a high refractive index. Further, since GZO and AZO are easily aligned along the c-axis, a crystal film is easily formed, and the stress of such a crystal film is increased, so that there are problems such as film peeling or film breakage.

Further, Patent Document 4 discloses a light-transmitting conductive material in which a wide range of refractive indices are realized by using ZnO and a fluorinated alkaline earth metal compound as main components. However, the light-transmitting conductive material is a crystalline film, and the effect of the amorphous film as described later in the present invention cannot be obtained. Further, Patent Document 5 discloses a transparent conductive film having a small refractive index and a small specific resistance and being amorphous, but the composition system is different from the present invention, and there is a possibility that the refractive index and the resistance value cannot be simultaneously adjusted. problem.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-008780

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-184876

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-238375

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2005-219982

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-035342

An object of the present invention is to provide a sintered body which can obtain a transparent conductive film which can maintain good visible light transmittance and conductivity, and in particular, an amorphous film which can obtain a low refractive index. The film has high transmittance and excellent mechanical properties, and thus can be used as a transparent conductive film for a display or a protective film for an optical disk. Thereby, the characteristics of the optical element are improved, the equipment cost is lowered, and the film forming property is greatly improved, which is the object of the present invention.

In order to solve the above problems, the inventors of the present invention conducted intensive studies, and as a result, found that the resistivity and the refractive index can be arbitrarily adjusted by replacing a conventional transparent conductive film of ITO or the like with the material system disclosed below. It can ensure the optical characteristics equivalent or better than the conventional ones, and can be stably formed by sputtering or ion plating, and by forming an amorphous film, the characteristics of the optical element having the film can be improved and produced. Sexual improvement.

The present invention provides the following invention in view of this finding.

1) A sintered body comprising zinc (Zn), a trivalent metal element, germanium (Ge), and/or germanium (Si) or oxygen (O), and the total content of the trivalent metal element is determined in terms of oxide. When the total content of A mol%, Ge, and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , 15 A+B 70.

2) The sintered body according to the above 1), wherein the total content of the Ge and/or Si is 5 B 30.

The sintered body according to the above 1), wherein the total content of the trivalent metal element is 0.1 or more in terms of the atomic ratio of the trivalent metal element / (Zn + trivalent metal element).

The sintered body according to any one of the above 1 to 3, wherein the trivalent metal element is selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), ytterbium (Y), and indium (In ) one or more elements in the group.

5) A sintered body composed of an oxide of zinc (Zn), gallium (Ga), or germanium (Ge), and the content of Ga is set to A mol% in terms of Ga 2 O 3 , and the content of Ge is converted into GeO 2 . When B mol% is set and the remaining part is set to ZnO, it satisfies 15 A+B 50 and A 3B/2 conditions.

The sintered body according to any one of the above 1 to 5, further comprising a metal in an amount of 0.1 to 5 wt% in terms of oxide weight, the metal forming an oxide having a melting point of 1000 ° C or less.

(7) The sintered body according to the above 6), wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , one or more oxides of the group consisting of Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .

8) The sintered body according to any one of the above 1) to 7), which has a relative density of 90% or more.

9) The sintered body according to any one of the above 1) to 8), which has a volume resistance value of 10 Ω ̇ cm or less.

10) A sputtering target using the sintered body of any one of the above 1) to 9).

11) An ion plating material using the sintered body described in the above 5).

12) A film comprising zinc (Zn), a trivalent metal element, germanium (Ge) and/or germanium (Si), and oxygen (O), and the total content of the trivalent metal element is determined as an oxide in terms of oxide. When the total content of mol%, Ge, and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , 15 A+B 70, and the film is an amorphous film.

13) A film comprising an oxide of zinc (Zn), gallium (Ga), or germanium (Ge), and a content of Ga is set to A mol% in terms of Ga 2 O 3 , and a content of Ge is set in GeO 2 conversion When B mol% and the remaining part is ZnO, it satisfies 15 A+B 50 and A Under the condition of 3B/2, the film is an amorphous film.

The film according to the above 12 or 13, further comprising a metal in an amount of 0.1 to 5 wt% in terms of oxide weight, the metal being formed from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5. One or more oxides of the group consisting of Sb 2 O 3 , TeO 2 , Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .

15) The film according to any one of the above 12), wherein the extinction coefficient at a wavelength of 450 nm is 0.01 or less.

The film according to any one of the above items 12) to 15), which has a refractive index of 2.00 or less at a wavelength of 550 nm.

17) The film according to any one of the above 12) to 16), which has a volume resistivity of from 1 × 10 -3 to 1 × 10 9 Ω ̇ cm.

18) A method for producing a sintered body, which is used for producing the sintered body according to any one of the above 1) to 9), which is obtained by mixing a raw material powder, and the obtained mixed powder is 1000 ° C in an inert gas or a vacuum atmosphere. After press sintering at 1500 ° C or press forming of the obtained mixed powder, the formed body is subjected to normal pressure sintering at 1000 ° C to 1500 ° C in an inert gas or vacuum atmosphere.

By replacing the conventional transparent conductive film of ITO or the like with the material shown in the above, the resistivity and the refractive index can be arbitrarily adjusted to ensure optical characteristics equivalent to or better than conventional ones, and sputtering or ion plating can be utilized. The film is formed stably and the film is formed into an amorphous film, whereby the characteristics of the optical element including the film can be improved and the productivity can be improved.

The present invention is a sintered body characterized by comprising zinc (Zn), a trivalent metal element, germanium (Ge) and/or germanium (Si), oxygen (O) as a constituent element, and a trivalent metal element. The total content is set to A mol% in terms of oxide, and the total content of Ge and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , and satisfies 15 A+B 70.

When the raw material is adjusted, the remaining portion is ZnO, and the ratio of each oxide is adjusted so that the total ratio of the respective oxides is 100 mol%. Therefore, the content of Zn can be obtained by converting the remaining portion of ZnO. Got it. By adjusting to such a composition, an amorphous film having a low refractive index can be formed, and the above effects of the present invention can be obtained.

Further, in the present invention, the content of each metal in the sintered body is determined in terms of oxide, and some or all of the metals in the sintered body exist as a composite oxide. Further, in the component analysis of the sintered body which is usually used, the content of each metal is not measured by measuring the content of the oxide.

The cerium oxide (GeO 2 ) and the cerium oxide (SiO 2 ) contained in the sintered body of the present invention are vitrified components (formation of an oxide of glass), and are effective components for amorphizing (glassizing) the film. On the other hand, the vitrification component reacts with zinc oxide (ZnO) to form a material such as ZnGe 2 O 4 to form a crystal film, and the film stress of such a crystal film increases, causing film peeling or film breakage. . Therefore, by introducing a trivalent metal element (described as M), a mullite composition (3M 2 O 3 -2GeO 2 or 3M 2 O 3 -2SiO 2 ) is formed, and it is expected that the formation of such a substance is inhibited.

In addition, since an oxide forming a glass such as yttrium oxide (GeO 2 ) or yttrium oxide (SiO 2 ) or an oxide of a trivalent metal element is a low refractive material as compared with zinc oxide (ZnO), by adding the An oxide that reduces the refractive index of the film. On the other hand, if the composition is adjusted so as to lower the refractive index (if ZnO is reduced), the resistance value tends to be high.

Therefore, when the total addition amount of the oxide of the trivalent metal element is (A), and the total addition amount of cerium oxide and/or cerium oxide is (B), it is set to 15 A+B 70. When A+B<15, it is difficult to form amorphous, which is not preferable. When A+B>70, the content of ZnO is reduced to become an insulating film, which is not preferable.

In the present invention, the content of the trivalent metal element is defined in terms of oxide, and when the trivalent metal element is referred to as M in the oxide herein, it means an oxide containing M 2 O 3 .

For example, in the case of the trivalent metal element aluminum (Al), it means an oxide containing Al 2 O 3 . The trivalent metal element is particularly preferably one or more elements selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), ytterbium (Y), and indium (In).

The trivalent metal element contributes to conductivity as a dopant of zinc oxide (ZnO), wherein the refractive indices of Al, Ga, B, Y, and In are lower, by combining with the above-described oxide forming glass. It is a particularly effective material because the refractive index and the resistance value can be easily adjusted. The oxides containing the metal elements may be separately added and compounded, and the object of the present invention can be achieved.

In the present invention, the total content of Ge and/or Si constituting the oxide forming the glass is preferably 5 mol% or more and 30 mol% or less, more preferably 5 mol% or more, in terms of GeO 2 and/or SiO 2 . Mol% or less. The reason for this is that if it is less than 5 mol%, the effect of lowering the refractive index becomes small, and a sufficient amorphization effect cannot be obtained. On the other hand, when it exceeds 30 mol% (20 mol%), the volume resistance of the sintered body tends to increase, and it is difficult to perform stable DC sputtering.

In the present invention, the total content of the trivalent metal element is preferably 0.1 or more, more preferably 0.15 or more, in terms of the atomic ratio of the trivalent metal element / (Zn + trivalent metal element). At this time, it is effective for low refractive index and amorphization. In order to exhibit this effect, the total content of the trivalent metal element is 0.1 or more, more preferably 0.15 or more in terms of an atomic ratio.

Further, the present invention provides a sintered body composed of an oxide of zinc (Zn), gallium (Ga), or germanium (Ge), and the content of Ga is set to A mol% in terms of Ga 2 O 3 , Ge. When the content is set to B mol% in terms of GeO 2 and the remaining portion is set to ZnO, it satisfies 15 A+B 50, and A 3B/2 conditions. A sintered body composed of this component is particularly useful as a material for ion plating.

The ion plating method is a technique in which a metal is evaporated in a vacuum by using an electron beam or the like, and a high potential plasma is ionized (cation), and a negative potential is applied to the substrate to accelerate the cation and adhere thereto to form a film. Compared with sputtering, ion plating has high material use efficiency and is expected to improve productivity.

When the sintered body of the present invention has a partial composition as described above, it can be used as an ion plating material. The reason for this is that by selecting the Ga or Ge element and the composition ratio, the vapor pressure or the like can be lowered to become ion-platable.

In the case of being used as an ion plating material, in addition to the plate shape formed by finishing the sintered body, the sintered body may be further pulverized to form a powder or a granule. The sintered body which is pulverized and formed into a powder or a granular form is more likely to evaporate than the plate-shaped sintered body, and therefore is more preferable from the viewpoint of production efficiency.

Further, the sintered body of the present invention may contain 0.1 to 5 wt% of a metal in terms of oxide weight, and the metal forms an oxide (low melting point oxide) having a melting point of 1000 ° C or less. Since zinc oxide (ZnO) is easily reduced and evaporated, there is a problem that the sintering temperature cannot be increased to a large extent, and it is difficult to increase the density of the sintered body. However, by adding such a low-melting-point oxide, it is possible to achieve an effect of increasing the density without greatly increasing the sintering temperature.

If the above metal is less than 0.1 wt%, the effect cannot be exhibited, and if it exceeds 5 wt%, If there is a change in characteristics, it is not good, so it is set within the above numerical range.

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, and Bi 2 O 3 . MoO 3 . These oxides can be added separately and in combination, and the object of the present invention can be achieved. The sintered body of the present invention can be used as a sputtering target, and in this case, the relative density is preferably 90% or more. The density increase improves the uniformity of the sputter film and suppresses the generation of particles during sputtering.

The sintered body of the present invention can have a bulk resistance of 10 Ω ̇ cm or less. High-speed film formation can be performed by direct current (DC) sputtering by lowering the bulk resistance value. Depending on the choice of materials, high frequency (RF) sputtering or magnetron sputtering is sometimes required, but even in this case the film formation speed is increased. By increasing the film formation speed, the production yield can be improved, which can greatly contribute to cost reduction.

In the present invention, it is important that a film obtained by sputtering a target obtained by processing a sintered body or a film formed by the above ion plating is amorphous (amorphous film). Whether or not the obtained film is an amorphous film can be judged by observing the diffraction intensity in the vicinity of 2θ = 34.4° of the occurrence peak of the (002) plane of ZnO by, for example, X-ray diffraction. The film having ZnO as a main component has a large film stress. Therefore, if it is a crystalline film, cracks or cracks occur, and problems such as film peeling occur. However, by forming the film into an amorphous film, it is possible to avoid the film. Excellent effect of problems such as cracking or cracking caused by 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. The film for a display is required to be transparent throughout the visible light region, but an oxide film such as an IZO film usually absorbs in a short-wavelength region, so that it is difficult to develop color. It is a distinct blue. According to the present invention, when the extinction coefficient at a wavelength of 450 nm is 0.01 or less, there is almost no absorption in a short-wavelength region, so that it is highly suitable as a material for a transparent material.

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 can achieve a refractive index of 2.00 or less at a wavelength of 550 nm (Comparative) Good for 1.90 or less). Further, the film has a volume resistivity of 1 × 10 -3 to 1 × 10 9 Ω ̇ cm.

Cerium oxide (GeO 2 ) or cerium oxide (SiO 2 ), an oxide composed of a trivalent metal element (wherein, Al 2 O 3 , Ga 2 O 3 , B 2 O 3 , Y 3 O 2 , In 2 O 3 ) Since a material having a low refractive index as compared with zinc oxide (ZnO), a film having a lower refractive index than a conventional film can be obtained by adding these oxides.

In addition, 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 be used as a transparent conductive film in various displays such as an organic EL television. Or an optical film forming a protective layer of the optical information recording medium. In the case of the protective layer of the optical information recording medium, in particular, since ZnS is not used, there is no contamination due to S, and there is no significant effect of deterioration of the recording layer caused thereby.

[Examples]

Hereinafter, description will be given based on examples and comparative examples. Furthermore, the present embodiment is merely an example at all, and the present invention is not limited by this example. That is, the present invention is only limited by the scope of the claims, and the present invention includes various modifications other than the embodiments included in the present invention.

(Example 1)

A ZnO powder, an Al 2 O 3 powder, an SiO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, these powders were blended at the blending ratios shown in Table 1, and after mixing them, the powder materials were subjected to hot press sintering under vacuum at a temperature of 1,100 ° C and a pressure of 250 kgf / cm 2 . Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 99.3%, the volume resistance was 2.1 mΩ ̇cm, and stable DC sputtering was possible.

In addition, sputtering is performed using the above-described finished target. The sputtering conditions were as follows: DC sputtering, sputtering power of 500 W, Ar gas pressure of 2 vol% of O 2 was set to 0.5 Pa, and film thickness was 1500 to 7000 Å. The amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, and extinction coefficient (wavelength: 450 nm) of the film-forming sample were measured. As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.80 (wavelength 550 nm), a volume resistivity of 2 × 10 8 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength 450). Nm), an amorphous film having a low refractive index is obtained.

(Example 2)

A ZnO powder, a Ga 2 O 3 powder, an SiO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing, the powder materials were subjected to hot press sintering under the conditions of an argon atmosphere at a temperature of 1,100 ° C and a pressure of 250 kgf / cm 2 . Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 98.5%, the volume resistance was 1.6 mΩ ̇cm, and stable DC sputtering was possible.

Further, using the above-mentioned finished target, sputtering was performed under the same conditions as in Example 1, and the amorphous (amorphous), refractive index (wavelength: 550 nm), and volume resistivity of the film-forming sample were measured. , extinction coefficient (wavelength 450 nm). As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.89 (wavelength 550 nm), a volume resistivity of 2 × 10 -1 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength). 450 nm), an amorphous film having a low refractive index is obtained.

(Example 3)

A ZnO powder, an Al 2 O 3 powder, a GeO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing, the powder materials were subjected to hot press sintering under the conditions of an argon atmosphere at a temperature of 1,100 ° C and a pressure of 250 kgf / cm 2 . Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 98.6%, the volume resistance was 3.6 mΩ ̇cm, and stable DC sputtering was possible.

Further, using the above-mentioned finished target, sputtering was performed under the same conditions as in Example 1, and the amorphous (amorphous), refractive index (wavelength: 550 nm), and volume resistivity of the film-forming sample were measured. , extinction coefficient (wavelength 450 nm). As shown in Table 1, the film formed by sputtering is an amorphous film having a refractive index of 1.79 (wavelength 550 nm), a volume resistivity of 5 × 10 6 Ω ̇ cm, and a nitrite coefficient of less than 0.01 (wavelength). 450 nm) is an amorphous film with a low refractive index.

(Example 4)

A ZnO powder, a Y 2 O 3 powder, a GeO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing, the powder materials were subjected to hot press sintering under the conditions of an argon atmosphere at a temperature of 1000 ° C and a pressure of 250 kgf / cm 2 . Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and the relative density of the obtained target were measured. As shown in Table 1, the relative density was 98.3%, and the volume resistance was 7.6 mΩ ̇cm, which was stable DC sputtering.

Further, using the above-mentioned finished target, sputtering was performed under the same conditions as in Example 1, and the amorphous (amorphous), refractive index (wavelength: 550 nm), and volume resistivity of the film-forming sample were measured. , extinction coefficient (wavelength 450 nm). As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.88 (wavelength 550 nm), a volume resistivity of 7 × 10 4 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength 450). Nm), an amorphous film having a low refractive index is obtained.

(Example 5)

A ZnO powder, an In 2 O 3 powder, and a GeO 2 powder were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing, the powder materials were subjected to hot press sintering under the conditions of an argon atmosphere at a temperature of 1050 ° C and a pressure of 250 kgf / cm 2 . Then, the sintered body is processed into a sputtering target shape by mechanical processing.

The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 98.7%, the volume resistance was 1.3 mΩ ̇cm, and stable DC sputtering was possible.

In addition, the same conditions as in Example 1 were used using the above-mentioned finished target. Under sputtering, the amorphous (amorphous), refractive index (wavelength 550 nm), volume resistivity, and extinction coefficient (wavelength: 450 nm) of the film-forming sample were measured.

As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.88 (wavelength 550 nm), a volume resistivity of 2 × 10 -3 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength). 450 nm), an amorphous film having a low refractive index is obtained.

(Example 6)

A ZnO powder, a B 2 O 3 powder, an SiO 2 powder, and a Bi 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing them, the powder materials were press-formed at a pressure of 500 kgf/cm 2 , and the formed bodies were subjected to vacuum at a temperature of 1300 ° C. Normal pressure sintering. Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 96.5%, the volume resistance was 2.3 Ω ̇cm, and stable DC sputtering was possible.

Further, using the above-mentioned finished target, sputtering was performed under the same conditions as in Example 1, and the amorphous (amorphous), refractive index (wavelength: 550 nm), and volume resistivity of the film-forming sample were measured. , extinction coefficient (wavelength 450 nm). As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.73 (wavelength 550 nm), a volume resistivity of 3 × 10 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength of 450 nm). ), an amorphous film having a low refractive index is obtained.

(Example 7)

A ZnO powder, a Ga 2 O 3 powder, a GeO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at the blending ratios shown in Table 1, and after mixing them, the powder materials were press-formed at a pressure of 500 kgf/cm 2 , and the molded bodies were placed in an argon atmosphere at a temperature of 1,100 ° C. Normal pressure sintering is carried out. Then, the sintered body is processed into a sputtering target shape by mechanical processing. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 99.8%, the volume resistance was 0.9 mΩ ̇cm, and stable DC sputtering was possible.

Further, using the above-mentioned finished target, sputtering was performed under the same conditions as in Example 1, and the amorphous (amorphous), refractive index (wavelength: 550 nm), and volume resistivity of the film-forming sample were measured. , extinction coefficient (wavelength 450 nm). As shown in Table 1, the thin film formed by sputtering is an amorphous film having a refractive index of 1.89 (wavelength 550 nm), a volume resistivity of 2 × 10 -3 Ω ̇ cm, and an extinction coefficient of less than 0.01 (wavelength). 450 nm), an amorphous film having a low refractive index is obtained.

(Comparative Example 1)

A ZnO powder, a Ga 2 O 3 powder, a GeO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at a blend ratio of A+B<15 as described in Table 1, and after mixing, the powder materials were placed under an argon atmosphere at a temperature of 1050 ° C under a pressure of 250 kgf/cm 2 . Hot press sintering is performed. Then, the sintered body is processed into a sputtering target shape by mechanical processing.

The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 95.8%, the volume resistance was 1.2 mΩ ̇cm, and DC sputtering was possible.

However, sputtering was performed under the same conditions as in Example 1 using the above-mentioned finished target, and the amorphous (amorphous), refractive index (wavelength 550 nm), and volume resistivity of the film-forming sample were measured. As a result of the extinction coefficient (wavelength of 450 nm), as shown in Table 1, the film formed by sputtering was not formed into an amorphous film. Further, the refractive index was 1.98 (wavelength 550 nm), the volume resistivity was 3 × 10 -3 Ω ̇ cm, and the extinction coefficient was less than 0.01 (wavelength: 450 nm).

(Comparative Example 2)

A ZnO powder, an Al 2 O 3 powder, an SiO 2 powder, and a B 2 O 3 powder as a low melting point oxide were prepared. Next, the powders were blended at a blend ratio of A+B>70 as described in Table 1, and after mixing them, the powder materials were placed under an argon atmosphere at a temperature of 1100 ° C and a pressure of 250 kgf/cm 2 . Hot press sintering is performed. Then, the sintered body is processed into a sputtering target shape by mechanical processing.

The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density was 96.4%, the volume resistance was 40 mΩ ̇cm, and DC sputtering was possible. However, sputtering was performed under the same conditions as in Example 1 using the above-mentioned finished target, and the amorphous (amorphous), refractive index (wavelength 550 nm), and volume resistivity of the film-forming sample were measured. As a result of the extinction coefficient (wavelength: 450 nm), as shown in Table 1, the volume resistivity of the film formed by sputtering was greater than 1 × 10 9 Ω ̇ cm, and the insulating property was exhibited. Further, the film is an amorphous film having a refractive index of 1.66 (wavelength 550 nm) and an extinction coefficient of less than 0.01 (wavelength: 450 nm).

(Example 8)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =80.0:13.0:7.0 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed as shown in Table 2, and the refractive index of the produced film was 1.87 (wavelength: 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 1 × 10 -2 Ω ̇ cm, indicating conductivity. Further, it was confirmed to be an amorphous film.

(Example 9)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =52.7:29.4:17.9 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed, and the refractive index of the produced film was 1.71 (wavelength: 550 nm).

Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 3 × 10 6 Ω ̇ cm, indicating conductivity. Further, it was confirmed to be an amorphous film.

(Embodiment 10)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =66.3:20.6:13.1 mol%, and after mixing, the powder material is placed in an argon environment. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed, and it was confirmed that the produced film was amorphous. In addition, the film has a refractive index of 1.75 (wavelength 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 6 × 10 4 Ω ̇ cm, indicating conductivity.

(Example 11)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =74.5:16.9:8.6 mol%, and after mixing, the powder material is placed in an argon environment. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed, and it was confirmed that the produced film was amorphous. In addition, the refractive index reaches 1.82 (wavelength 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 8 × 10 -2 Ω ̇ cm, indicating conductivity.

(Embodiment 12)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =67.7:23.4:8.9 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed, and it was confirmed that the produced film was amorphous. In addition, the refractive index of the film reached 1.77 (wavelength 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 3 × 10 -1 Ω ̇ cm, indicating conductivity.

(Example 13)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blend ratio of ZnO:Ga 2 O 3 :GeO 2 =50.2:41.9:7.9 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

When the sintered body was used for ion plating, stable ion plating was performed, and it was confirmed that the produced film was amorphous. In addition, the refractive index of the film reached 1.66 (wavelength 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 3 × 10 3 Ω ̇ cm, indicating conductivity.

(Comparative Example 3)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =85.0:2.2:12.8 mol%, and after mixing, the powder material is placed in an argon environment. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

By performing ion plating using this sintered body, stable ion plating was performed, and the refractive index of the film produced was 1.94 (wavelength 550 nm). Further, the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 4 × 10 -3 Ω ̇ cm, indicating conductivity. However, it was confirmed that the film was crystallized.

(Comparative Example 4)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =44.0:34.0:22.0 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

The sintered body was subjected to ion plating, and as a result, the film formed was amorphous, and the refractive index of the film was 1.68 (wavelength: 550 nm), the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was > 1 × 10 9 Ω ̇ cm, the conductivity is remarkably lowered.

(Comparative Example 5)

A ZnO powder of 5 μm or less corresponding to 3 N, a Ga 2 O 3 powder having an average particle diameter of 5 μm or less of 3 N, and a GeO 2 powder having an average particle diameter of 5 μm or less of 3 N are prepared. Next, the ZnO powder, the Ga 2 O 3 powder, and the GeO 2 powder are blended at a blending ratio of ZnO:Ga 2 O 3 :GeO 2 =90.0:7.0:3.0 mol%, and after mixing, the powder material is placed in an argon atmosphere. The hot-pressed sintering was carried out at a pressure of 850 ° C and 250 kgf / cm 2 to form a sintered body for ion plating.

The sintered body was subjected to ion plating, and as a result, the refractive index of the film was 1.93 (wavelength: 550 nm), the extinction coefficient was less than 0.01 (wavelength: 450 nm), and the volume resistivity of the film was 1 × 10 -3 Ω ̇ cm, which showed conductivity. Sex, but the film produced is crystallized.

[Industrial availability]

The sintered body of the present invention can be used as a sputtering target or an ion plating material, and a film formed using the sputtering target or the ion plating material has the following effects: when forming a transparent conductive film or a protective film for a disc in various displays It has extremely excellent characteristics in terms of transmittance, refractive index, and electrical conductivity. Further, the present invention is characterized in that it is excellent in cracking or etching performance of the film by being formed into an amorphous film.

Further, the sputtering target using the sintered body of the present invention has a low bulk resistance value and a high density of 90% or more, so that stable DC sputtering can be performed. Further, it has a remarkable effect that the sputtering controllability as a feature of the DC sputtering can be easily obtained, and the deposition rate can be improved and the sputtering efficiency can be improved. RF sputtering will also be carried out as needed, but at this time, the film formation speed is also improved. In addition, It can reduce the particles (dust) or nodule generated during sputtering at the time of film formation, and the quality is less uneven, which can improve mass productivity.

Further, since the ion plating material of 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 or cracks due to film stress and film peeling. Such an amorphous film is particularly useful as an optical film for forming a protective layer of an optical information recording medium, a film for an organic EL television, and a film for a transparent electrode.

Claims (21)

  1. A sintered body containing zinc (Zn), a trivalent metal element, germanium (Ge) and/or germanium (Si), and oxygen (O), and the total content of the trivalent metal element is changed to a mol in terms of oxide. When the total content of %, Ge, and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , 15 A+B 70; the total content B of the Ge and/or Si is 5 in terms of GeO 2 and/or SiO 2 B 30; The total content of the trivalent metal element is 0.1 or more in terms of the atomic ratio of the trivalent metal element / (Zn + trivalent metal element).
  2. The sintered body of claim 1, wherein the trivalent metal element is selected from the group consisting of aluminum (Al), gallium (Ga), boron (B), ytterbium (Y), and indium (In). More than one element.
  3. A sintered body containing an oxide of zinc (Zn), gallium (Ga), or germanium (Ge) and containing no indium (In), and the content of Ga is set to A mol%, Ge in terms of Ga 2 O 3 When the content is set to B mol% in terms of GeO 2 and the remaining portion is ZnO, it satisfies 15 A+B 50 and A 3B/2 conditions.
  4. The sintered body according to any one of claims 1 to 3, further comprising 0.1 to 5 wt% of a metal in terms of oxide weight, the metal forming an oxide having a melting point of 1000 ° C or less.
  5. The sintered body of claim 4, wherein the oxide having a melting point of 1000 ° C or less is selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5 , Sb 2 O 3 , TeO 2 , one or more oxides of the group consisting of Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .
  6. The sintered body of the fourth aspect of the patent application has a relative density of 90% or more.
  7. The sintered body of the fifth aspect of the patent application has a relative density of 90% or more.
  8. The sintered body according to any one of claims 1 to 3, which has a volume resistance value of 10 Ω ̇ cm or less.
  9. The sintered body of the fourth aspect of the patent application has a volume resistance value of 10 Ω ̇ cm or less.
  10. The sintered body of the fifth aspect of the patent application has a bulk resistance value of 10 Ω ̇ cm or less.
  11. A sputtering target using the sintered body of claim 1 or 2.
  12. A sputtering target using the sintered body of claim 4 of the patent application.
  13. A sputtering target using the sintered body of claim 5 of the patent application.
  14. An ion plating material using the sintered body of claim 3 of the patent application.
  15. A film containing zinc (Zn), a trivalent metal element, germanium (Ge) and/or germanium (Si), and oxygen (O), and the total content of the trivalent metal element is determined to be A mol% in terms of oxide. When the total content of Ge, and/or Si is set to B mol% in terms of GeO 2 and/or SiO 2 , 15 A+B 70, and the film is an amorphous film; the total content B of the Ge and/or Si is 5 in terms of GeO 2 and/or SiO 2 B 30; The total content of the trivalent metal element is 0.1 or more in terms of the atomic ratio of the trivalent metal element / (Zn + trivalent metal element).
  16. A thin film containing an oxide of zinc (Zn), gallium (Ga), or germanium (Ge) and containing no indium (In), and the content of Ga is set to A mol% in terms of Ga 2 O 3 , Ge When the content is set to B mol% in terms of GeO 2 and the remaining portion is set to ZnO, it satisfies 15 A+B 50 and A Under the condition of 3B/2, the film is an amorphous film.
  17. The film of claim 15 or 16, further comprising 0.1 to 5 wt% of metal in terms of oxide weight, the metal being selected from the group consisting of B 2 O 3 , P 2 O 5 , K 2 O, V 2 O 5. One or more oxides of the group consisting of Sb 2 O 3 , TeO 2 , Ti 2 O 3 , PbO, Bi 2 O 3 , and MoO 3 .
  18. The film of claim 15 or 16 has an extinction coefficient of 0.01 or less at a wavelength of 450 nm.
  19. The film of claim 15 or 16 has a refractive index of 2.00 or less at a wavelength of 550 nm.
  20. The film of claim 15 or 16 has a volume resistivity of 1 × 10 -3 to 1 × 10 9 Ω ̇ cm.
  21. A method for producing a sintered body, which is used for producing the sintered body according to any one of claims 1 to 10, which is a method of mixing a raw material powder, and mixing the obtained mixed powder in an inert gas or a vacuum atmosphere at 1000 ° C. After press sintering at 1500 ° C or press forming of the obtained mixed powder, the formed body is subjected to normal pressure sintering at 1000 ° C to 1500 ° C in an inert gas or vacuum atmosphere.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0845352A (en) * 1994-08-02 1996-02-16 Sekisui Chem Co Ltd Transparent conductor
US5955178A (en) * 1994-06-10 1999-09-21 Hoya Corporation Electro-conductive oxides and electrodes using the same
WO2009145152A1 (en) * 2008-05-27 2009-12-03 株式会社カネカ Transparent conductive film and method for producing the same
TW201119971A (en) * 2009-09-30 2011-06-16 Idemitsu Kosan Co Sintered in-ga-zn-o-type oxide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
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JP5388266B2 (en) * 2008-03-19 2014-01-15 国立大学法人岩手大学 ZnO-based target and manufacturing method thereof, conductive thin film manufacturing method, and conductive thin film
WO2010070832A1 (en) * 2008-12-15 2010-06-24 出光興産株式会社 Sintered complex oxide and sputtering target comprising same
JP2012124446A (en) * 2010-04-07 2012-06-28 Kobe Steel Ltd Oxide for semiconductor layer of thin film transistor and sputtering target, and thin film transistor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5955178A (en) * 1994-06-10 1999-09-21 Hoya Corporation Electro-conductive oxides and electrodes using the same
JPH0845352A (en) * 1994-08-02 1996-02-16 Sekisui Chem Co Ltd Transparent conductor
WO2009145152A1 (en) * 2008-05-27 2009-12-03 株式会社カネカ Transparent conductive film and method for producing the same
TW201119971A (en) * 2009-09-30 2011-06-16 Idemitsu Kosan Co Sintered in-ga-zn-o-type oxide

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