WO2014112209A1 - Sintered compact for fabricating amorphous transparent electroconductive film having low refractive index, and amorphous transparent electroconductive film having low refractive index - Google Patents

Abstract

A sintered compact characterized by comprising: zinc (Zn); gallium (Ga), aluminum (Al), or boron (B); germanium (Ge) or silicon (Si); magnesium (Mg); oxygen (O); and fluorine (F); and in satisfying the relationship 10 ≤ A + B + C ≤ 70, where A is the content of gallium (Ga), aluminum (Al), or boron (B) converted to mol% in terms of Ga₂O₃, Al₂O₃, or B₂O₃, B is the content of germanium (Ge) or silicon (Si) converted to mol% in terms of GeO₂ or SiO₂, and C is the content of magnesium (Mg) converted to mol% in terms of MgF₂. In particular, a low-refractive-index amorphous thin film can be formed which has low bulk resistance and is capable of DC sputtering.

Description

Sintered body for producing low refractive index amorphous transparent conductive film and low refractive index amorphous transparent conductive 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.

When using visible light in various optical devices such as displays and touch panels, the material needs to be transparent, and it is particularly preferable that the transmittance is high in the entire visible light region. In addition, if the refractive index is high, light loss increases or the viewing angle dependency of a display or the like deteriorates. Therefore, the refractive index is low, and it is amorphous to improve film cracking and etching performance. It is desired to be a membrane.

Since the amorphous film has low stress, cracks are less likely to occur compared to the crystal film, and it is considered that the amorphous film will be required for display applications toward flexible use. ITO (indium oxide-tin oxide) is known as a transparent and conductive material. However, ITO needs to crystallize the film in order to improve conductivity and transmittance, and if it is amorphous, there is a problem that it has absorption in a short wavelength region and does not become a transparent film.

As materials similar to those described above, 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. Also, GZO and AZO easily become crystallized films due to the ease of c-axis orientation of ZnO and the formation of ZnGe ₂ O ₄ , and such crystallized films increase stress, so that film peeling or film cracking occurs. There are problems such as.

Further, Patent Document 4 discloses a light-transmitting conductive material that realizes a wide 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 a high transmittance and excellent mechanical properties, it is useful as a thin film for optical devices, particularly as an optical adjustment thin film. 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 adopting the material system presented below, it becomes possible to arbitrarily adjust the resistivity and the refractive index. In addition to ensuring the optical characteristics of the film, it is possible to form a stable film by sputtering or ion plating. By using an amorphous film, it is possible to improve the characteristics and productivity of an optical device including the thin film. And gained knowledge.

Based on this finding, the present invention provides the following inventions.
1) zinc (Zn), gallium (Ga) or aluminum (Al) or boron (B), germanium (Ge) or silicon (Si), magnesium (Mg), and oxygen (O), and, fluorine consist (F), gallium (Ga) or aluminum (Al) or boron Amol% in the content of (B) is Ga ₂ O ₃ or Al ₂ O ₃ or terms _of B ₂ O _3, germanium (Ge) Or, when the content of silicon (Si) is Bmol% in terms of GeO ₂ or SiO _{2 and} the content of magnesium (Mg) is C mol% in terms of MgF ₂ , the firing is characterized by 10 ≦ A + B + C ≦ 70 Union,
2) It consists of zinc (Zn), gallium (Ga), germanium (Ge), magnesium (Mg), oxygen (O), and fluorine (F), and the content of gallium (Ga) is Ga ₂ O _3. 10 ≦ A + B + C ≦ 70, where Amol% in terms of conversion, germanium (Ge) content is Bmol% in terms of GeO ₂ , and magnesium (Mg) content is Cmol% in terms of MgF _2. The sintered body according to 1) above,
3) Furthermore, when A> B and the content of zinc (Zn) is Dmol% in terms of ZnO, D> A + B, wherein the sintered body according to 1) or 2) above,
4) The sintering according to any one of 1) to 3) 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. body,
5) The oxides having a melting point of 1000 ° C. or less are 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 4) above, which is one or more oxides selected from the group of MoO ₃ ,
6) The sintered body according to any one of 1) to 5) above, wherein the relative density is 90% or more,
7) The sintered body according to any one of 1) to 6) above, wherein the bulk resistance is 10 Ω · cm or less,
8) A sputtering target using the sintered body described in 1) to 6) above,
9) An ion plating material using the sintered body described in 2) to 6) above,

The present invention also provides:
10) Zinc (Zn) and Gallium (Ga) or Aluminum (Al) or Boron (B), Germanium (Ge) or Silicon (Si), Magnesium (Mg), and Oxygen (O), And a thin film made of fluorine (F) and characterized by being amorphous,
11) The thin film as described in 10) above, which is made of zinc (Zn), gallium (Ga), germanium (Ge), magnesium (Mg), oxygen (O), and fluorine (F), and is amorphous.
12) The thin film according to 10) or 11), further comprising a metal that forms an oxide having a melting point of 1000 ° C. or lower,
13) The oxides having a melting point of 1000 ° C. or lower are 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 12) above, which is one or more oxides selected from the group of MoO ₃
14) The thin film according to 12) or 13) above, which contains 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,
15) A thin film formed using the sputtering target described in 8) above, which is an amorphous film,
16) A thin film formed using the ion plating material described in 9) above, which is an amorphous film,
17) The thin film as described in any one of 10) to 16) above, wherein the refractive index at a wavelength of 550 nm is 2.00 or less,
18) The thin film according to any one of 10) to 17) above, wherein the extinction coefficient at a wavelength of 450 nm is 0.01 or less,
19) The thin film according to any one of 10) to 18) above, which has a volume resistivity of 1 × 10 ⁻³ to 1 × 10 ⁹ Ω · cm.

According to the present invention, by adopting the material system shown above, it is possible to arbitrarily adjust the resistivity and the refractive index, and it is possible to ensure desired optical characteristics, as well as sputtering and ion plating. Can be stably formed, and by using an amorphous film, it is possible to improve the characteristics and productivity of an optical device including the film.

The present invention includes 1) zinc (Zn), 2) gallium (Ga) or aluminum (Al) or boron (B), 3) germanium (Ge) or silicon (Si), 4) magnesium (Mg), and 5) oxygen. (O), 6) A sintered body containing fluorine (F) as a constituent element.
What is important in the present invention is that the content of gallium (Ga), aluminum (Al) or boron (B) in 2) above is calculated in terms of Ga ₂ O _3, Al ₂ O ₃ or B ₂ O ₃ , respectively. and Amol%, the content of germanium (Ge) or silicon (Si), when each and Bmol% by GeO ₂ terms or in terms of SiO _2, was C mol% content of magnesium (Mg) in MgF ₂ terms, It is characterized by satisfying 10 ≦ A + B + C ≦ 70. Thereby, a favorable resistivity and refractive index can be obtained.

The content of Zn can be determined from the ZnO equivalent of the remainder because the remainder is ZnO and the ratio of each oxide is adjusted to a total of 100 mol% in the raw material adjustment. By setting it as such a composition, the amorphous film of a low refractive index can be produced 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 oxide or fluoride. However, a part of each metal in the sintered body exists as a composite oxide. ing. Moreover, in the component analysis used normally of a sintered compact, each content is measured not as an oxide or fluoride but as a metal.

Since germanium oxide (GeO ₂ ) and silicon dioxide (SiO ₂ ) contained in the sintered body of the present invention are vitrification components, the thin film can be made amorphous (vitrified). On the other hand, germanium oxide (GeO ₂ ), such as these vitrification components, tends to form a crystallized film by forming zinc oxide (ZnO) and ZnGe ₂ O _4, and such a crystallized film has a large film stress. Cause film peeling and film cracking. Therefore, by introducing gallium oxide (Ga ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), and boron oxide (B ₂ O ₃ ), a mullite composition (for example, 3Ga ₂ O ₃ -2GeO ₂ ) is formed. Therefore, it can be expected to inhibit the production of ZnGe ₂ O _{4 and the} like.

By the way, gallium oxide (Ga ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), boron oxide (B ₂ O ₃ ), germanium oxide (GeO ₂ ), and silicon dioxide (SiO ₂ ) are zinc oxide (ZnO). The refractive index of the film can be lowered by adding these oxides. 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, so it is extremely difficult to adjust both the resistance value and the refractive index. .

Therefore, by using a quaternary composition in which magnesium fluoride (MgF ₂ ) is further added to the ternary composition, the refractive index can be lowered while suppressing an increase in resistivity.
When MgF ₂ is added, the resistance value tends to increase, but since the refractive index is lower than the other three components, the refractive index can be lowered even with a small amount of addition, and an increase in resistance value can be suppressed. . Further, since MgF ₂ is an optically transparent material, the addition does not reduce the transmittance and does not hinder the amorphization. The addition amount of MgF ₂ can be determined in consideration of the resistance value and the refractive index, but is preferably 50 mol% or less.

Further, in the sintered body of the present invention, in order to increase the abundance ratio of the mullite composition described above, the oxidation of gallium, aluminum, or boron with respect to the oxide equivalent content (Bmol%) of germanium or silicon. It is preferable to increase the content (Amol%) in terms of physical properties. Thereby, formation of ZnGe ₂ O ₄ can be suppressed, and crystallization of the film can be suppressed.
In order to secure the resistance value of the film, the total of the oxide equivalent content (A mol%) of gallium, aluminum or boron and the oxide equivalent content (B mol%) of germanium or silicon Thus, it is preferable to increase the content (Dmol%) of zinc oxide in terms of ZnO.

Furthermore, it is effective for the sintered body of the present invention to contain a metal that forms an oxide having a melting point of 1000 ° C. or lower (low melting point oxide). 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.
In order to improve the density of the sintered body, it is important to sinter the low melting point oxide in a liquid phase state. In order to accelerate the reaction of the raw material powder, calcining after adding a low melting point oxide may be considered. However, when calcining, the low melting point oxide forms a solid solution or forms a composite oxide with zinc oxide. As a result, the melting point becomes higher than the original melting point of the low melting point oxide, and the effect of increasing the density may not be obtained. Therefore, after adding the low melting point oxide, it is very important to perform pressure sintering such as hot pressing without calcining.

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.
The metal forming the low melting point oxide is preferably contained in an amount of 0.1 to 5 wt% in terms of oxide weight. If it is less than 0.1 wt%, the effect cannot be sufficiently exhibited, and if it exceeds 5 wt%, the characteristics may vary depending on the composition, which is not preferable.

When the sintered body of the present invention is used as a sputtering target, 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.
In addition, the sintered body of the present invention can achieve a bulk resistance of 10 Ω · cm or less. Reduction of the bulk resistance value enables high-speed film formation by direct current (DC) sputtering. 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 be used as an ion plating material in addition to the above sputtering target. The ion plating method is a method in which a metal is evaporated with an electron beam in a vacuum, ionized with high-frequency plasma or vacuum discharge, and a negative potential is applied to a substrate to accelerate and attach cations to form a film. Yes (Science and Chemistry Dictionary). When film formation is performed using the ion plating method, if the evaporation raw material for ion plating and the composition of the film match, the evaporation raw material can be used as it is for ion plating. There is an advantage that it can be operated.
In particular, in the present invention, gallium oxide (Ga ₂ O ₃ ), germanium oxide (GeO ₂ ), and magnesium fluoride (MgF ₂ ) have a vapor pressure similar to that of zinc oxide (ZnO). Suitable material.

The sintered body of the present invention can efficiently form a thin film having excellent characteristics by utilizing a vapor phase growth method such as the sputtering method or the ion plating method as described above. In particular, it is useful for industrially producing a low refractive index optical thin film having a refractive index of 2.00 or less (light wavelength of 550 nm).

The thin film formed using the sintered body of the present invention is 1) zinc (Zn), 2) gallium (Ga) or aluminum (Al) or boron (B), 3) germanium (Ge) or silicon (Si), 4) Magnesium (Mg), 5) Oxygen (O), 6) An amorphous film having fluorine (F) as a constituent element.
Magnesium is contained in the sintered body as a fluoride, but magnesium fluoride forms a complex oxide with zinc, gallium, and germanium, most of which is magnesium as a film. On the other hand, part of the fluorine remains in the film and does not completely desorb.

As described above, in a ternary system such as ZnO—Ga ₂ O ₃ —GeO ₂ , when the composition is adjusted so as to reduce the refractive index (adjusted so as to reduce ZnO), the resistance value tends to increase. By introducing magnesium fluoride (MgF ₂ ), the refractive index can be lowered while suppressing an increase in resistance value. In particular, the thin film of the present invention can realize a refractive index at a wavelength of 550 nm of 2.00 or less and a volume resistivity of 1 × 10 ⁻³ to 1 × 10 ⁹ Ω · cm.

Moreover, the thin film formed using the sintered body of the present invention can achieve an extinction coefficient of 0.01 or less at a wavelength of 450 nm. Thin films for optical devices such as displays and touch panels need to be transparent over the entire visible light range, but oxide films such as IZO films generally absorb in the short wavelength range, so they produce a clear blue color. It was difficult to make. However, 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.

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.

(Example 1)
After using ZnO powder, Ga ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder as basic raw materials, and adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition B ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, hot press sintering was performed under conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Then, this sintered body was finished into a sputtering target shape having a diameter of 6 inches and a thickness of 5 cm by machining.
The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 99.8%, the bulk resistance was 4.2 mΩ · cm, and stable DC sputtering was possible. Further, sputtering was performed using the finished target. The sputtering conditions, DC sputtering, sputtering power 500 W, the O ₂ and Ar gas pressure 0.5Pa containing 0 ~ 2 vol%, was formed to a thickness of 1500 ~ 7000 Å. 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 Table 2, the thin film formed by sputtering is an amorphous film, the refractive index is 1.75 (wavelength 550 nm), the volume resistivity is> 1 × 10 ⁶ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

(Example 2)
ZnO powder, Al ₂ O ₃ powder, GeO ₂ powder, MgF ₂ powder are used as basic raw materials, and after adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition B ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 98.9%, the bulk resistance was 16 mΩ · cm, and stable DC sputtering was possible.
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. As shown in Table 2, the thin film formed by sputtering is an amorphous film, the refractive index is 1.71 (wavelength 550 nm), the volume resistivity is> 1 × 10 ⁷ Ω · cm, and the extinction coefficient is 0.01. And an amorphous film having a low refractive index (wavelength 450 nm).

(Example 3)
ZnO powder, Ga ₂ O ₃ powder, SiO ₂ powder, and MgF ₂ powder are used as basic raw materials, and after adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition Bi ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, it press-molded with the pressure of 500 kgf / cm < ² >. After pressure molding, atmospheric pressure sintering was performed at 1400 ° C. in the atmosphere, and this sintered body was finished into a sputtering target shape by machining. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 96.3%, the bulk resistance was 45 mΩ · cm, and stable DC sputtering was possible.
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. As shown in Table 2, the thin film formed by sputtering is an amorphous film, the refractive index is 1.65 (wavelength 550 nm), the volume resistivity is> × 10 ⁸ Ω · cm, and the extinction coefficient is less than 0.01. An amorphous film having a low refractive index (wavelength 450 nm) was obtained.

Example 4
ZnO powder, Ga ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder were used as basic raw materials, and as shown in Table 1, the ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, the sintered body was pulverized to finish an ion plating material having a particle size of 1 to 6 mm.
Using the above ion plating material, ion plating was performed in a 2% O ₂ atmosphere to form a film having a thickness of 1500 to 7000 mm. 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 Table 2, the thin film formed by ion plating is an amorphous film, the refractive index is 1.80 (wavelength 550 nm), the volume resistivity is> 1 × 10 ² Ω · cm, and the extinction coefficient is 0. An amorphous film having a low refractive index of less than 0.01 (wavelength 450 nm) was obtained.

(Example 5)
After using ZnO powder, Al ₂ O ₃ powder, SiO ₂ powder, and MgF ₂ powder as basic raw materials and adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition B ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 98.4%, the bulk resistance was 2.3 mΩ · cm, and stable DC sputtering was possible.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is an amorphous film. The refractive index is 1.91 (wavelength 550 nm), the volume resistivity is 1 × 10 ⁰ Ω · cm, the extinction coefficient is less than 0.01 (wavelength 450 nm), and an amorphous film having a low refractive index is obtained. It was.

(Example 6)
ZnO powder, Ga ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder were used as basic raw materials, and as shown in Table 1, the ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, the sintered body was pulverized to finish an ion plating material having a particle size of 1 to 6 mm.
Using the above ion plating material, ion plating was performed under the same conditions as in Example 4. 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 2, the thin film formed by ion plating was An amorphous film having a refractive index of 1.82 (wavelength 550 nm), a volume resistivity> 1 × 10 ³ Ω · cm, an extinction coefficient of less than 0.01 (wavelength 450 nm), and a low refractive index amorphous film was gotten.

(Example 7)
After using ZnO powder, Al ₂ O ₃ powder, SiO ₂ powder, and MgF ₂ powder as basic raw materials and adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition B ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 99.2%, the bulk resistance was 5.4 mΩ · cm, and stable DC sputtering was possible.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is an amorphous film. The refractive index is 1.82 (wavelength 550 nm), the volume resistivity is> 1 × 10 ² Ω · cm, and the extinction coefficient is less than 0.01 (wavelength 450 nm). Obtained.

(Example 8)
ZnO powder, Ga ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder were used as basic raw materials, and as shown in Table 1, the ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under conditions of a temperature of 1050 ° C. and a pressure of 250 kgf / cm ² . Thereafter, the sintered body was pulverized to finish an ion plating material having a particle size of 1 to 6 mm.
Using the above ion plating material, ion plating was performed under the same conditions as in Example 4. 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 2, the thin film formed by ion plating was An amorphous film having a refractive index of 1.82 (wavelength 550 nm), a volume resistivity> 1 × 10 ³ Ω · cm, an extinction coefficient of less than 0.01 (wavelength 450 nm), and a low refractive index amorphous film was gotten.

Example 9
After using ZnO powder, B ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder as basic raw materials, and adjusting the ratio of the basic raw materials so that the total amount becomes 100 mol% as shown in Table 1, this basic composition B ₂ O ₃ powder, which is a low melting point oxide, was added at a ratio shown in Table 1. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 99.3%, the bulk resistance was 7.2 mΩ · cm, and stable DC sputtering was possible.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is an amorphous film. The refractive index is 1.74 (wavelength 550 nm), the volume resistivity is> 1 × 10 ² Ω · cm, and the extinction coefficient is less than 0.01 (wavelength 450 nm). Obtained.

(Example 10)
ZnO powder, B ₂ O ₃ powder, GeO ₂ powder, and MgF ₂ powder were used as basic raw materials, and as shown in Table 1, the ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance and relative density of the obtained target were measured. As shown in Table 1, the relative density reached 93.8%, the bulk resistance was 12 mΩ · cm, and stable DC sputtering was possible.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is an amorphous film. The refractive index is 1.74 (wavelength 550 nm), the volume resistivity is> 1 × 10 ² Ω · cm, and the extinction coefficient is less than 0.01 (wavelength 450 nm). Obtained.

(Comparative Example 1)
As an example in which MgF ₂ powder is not added and the condition of A + B + C <70 is not satisfied, Comparative Example 1 uses ZnO powder, Al ₂ O ₃ powder, and SiO ₂ powder as basic raw materials, and these are shown in Table 1. The ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance of the obtained target was measured. As shown in Table 1, the bulk resistance was as high as 13 mΩ · cm.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is refracted. The resistivity was 1.75, but the resistivity increased remarkably as the volume resistivity exceeded 1 × 10 ⁹ Ω · cm.

(Comparative Example 2)
As an example in which MgF ₂ powder is not added and the condition of 10 <A + B + C is not satisfied, Comparative Example 2 uses ZnO powder, Ga ₂ O ₃ powder, and GeO ₂ powder as basic raw materials, and these are shown in Table 1. The ratio of the basic raw materials was adjusted so that the total amount was 100 mol%. Next, after mixing this, hot press sintering was performed under 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. The bulk resistance of the obtained target was measured. As shown in Table 1, the bulk resistance was 1.5 mΩ · cm.
Further, sputtering was performed under the same conditions as in Example 1 using the finished target. 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 2, the thin film formed by sputtering is amorphous. It did not become a film.

The sintered body of the present invention can be used as a sputtering target, and the thin film formed using the sputtering target forms a part of the structure of a transparent conductive film for optical adjustment in a display or a touch panel or an optical disk. There is an effect that it has 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.
The sputtering target using the sintered body of the present invention has a low bulk resistance value and a high relative density of 90% or more, and thus enables stable DC sputtering. 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, the sintered body of the present invention can be used not only as a sputtering target but also as an ion beam evaporation material. As the ion beam deposition material, the sintered body can be further crushed and used as a granular material or a powdery material. Formation of a thin film by ion beam evaporation can be more easily performed by controlling the change in vapor pressure, and is effective for forming a film. In this way, there is a remarkable effect that a film for optical adjustment of an optical device can be stably manufactured at low cost.

Claims (19)

1. Zinc (Zn), gallium (Ga) or aluminum (Al) or boron (B), germanium (Ge) or silicon (Si), magnesium (Mg), oxygen (O), and consists fluorine (F), gallium (Ga) or aluminum (Al) or boron (B) Amol% content is Ga ₂ O ₃ or Al ₂ O ₃ or terms _of B ₂ O _3, and germanium (Ge) or silicon Bmol% content is GeO ₂ or SiO ₂ in terms of (Si), when the content of magnesium (Mg) has a C mol% with MgF ₂ terms, the sintered body, which is a 10 ≦ a + B + C ≦ 70 .
2. It consists of zinc (Zn), gallium (Ga), germanium (Ge), magnesium (Mg), oxygen (O), and fluorine (F), and the content of gallium (Ga) in terms of Ga ₂ O ₃ Amol%, Bmol% content is GeO ₂ conversion germanium (Ge), when the content of magnesium (Mg) has a C mol% with MgF ₂ terms, claims, characterized in that a 10 ≦ a + B + C ≦ 70 1. The sintered body according to 1.
3. Furthermore, it is A> B and it is D> A + B when content of zinc (Zn) is Dmol% in conversion of ZnO, The sintered body according to claim 1 or 2 characterized by things.
4. The sintered body according to any one of claims 1 to 3, 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.
5. The oxides having a melting point of 1000 ° C. or less 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 , The sintered body according to claim 4, wherein the sintered body is one or more oxides selected from the group of MoO ₃ .
6. The sintered body according to any one of claims 1 to 5, wherein the relative density is 90% or more.
7. The sintered body according to any one of claims 1 to 6, wherein the bulk resistance is 10 Ω · cm or less.
8. A sputtering target using the sintered body according to any one of claims 1 to 6.
9. An ion plating material using the sintered body according to any one of claims 2 to 6.
10. Zinc (Zn), gallium (Ga) or aluminum (Al) or boron (B), germanium (Ge) or silicon (Si), magnesium (Mg), oxygen (O), and A thin film made of fluorine (F) and characterized by being amorphous.
11. The thin film according to claim 10, wherein the thin film is made of zinc (Zn), gallium (Ga), germanium (Ge), magnesium (Mg), oxygen (O), and fluorine (F), and is amorphous.
12. Furthermore, the thin film of Claim 10 or 11 containing the metal which forms an oxide whose melting | fusing point is 1000 degrees C or less.
13. The oxides having a melting point of 1000 ° C. or less 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 , The thin film according to claim 12, wherein the thin film is one or more oxides selected from the group of MoO ₃ .
14. 14. The thin film according to claim 12, wherein the metal forming an oxide having a melting point of 1000 ° C. or less is contained in an amount of 0.1 to 5 wt% in terms of oxide weight.
15. A thin film formed using the sputtering target according to claim 8, wherein the thin film is an amorphous film.
16. A thin film formed using the ion plating material according to claim 9, wherein the thin film is an amorphous film.
17. The thin film according to any one of claims 10 to 16, wherein a refractive index at a wavelength of 550 nm is 2.00 or less.
18. The thin film according to any one of claims 10 to 17, wherein an extinction coefficient at a wavelength of 450 nm is 0.01 or less.
19. 19. The thin film according to claim 10, wherein the volume resistivity is 1 × 10 ⁻³ to 1 × 10 ⁹ Ω · cm.