TW201348177A - Sintered object for forming low-refractive-index film and process for producing same - Google Patents

Abstract

A sintered object which comprises zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized by containing the fluoride of magnesium (Mg) in an amount of 1.0-27 mol% in terms of Mg element amount. Provided, on the basis of this sintered object, is a sintered object which can be used in forming a thin film for use as an electrode for flexible displays, organic EL televisions, or touch panels, as an optical thin film for forming the protective layer, reflection layer, or semi-transparent layer of an optical information recording medium, or as the seed layer of a hard disk. With the sintered object, it is possible to provide a thin film which is optimal for such applications and which is amorphous, has such a satisfactory visible light transmittance that the extinction coefficient is 0.01 or lower (wavelength, 450 nm), and has a refractive index as low as 2.0 or less.

Description

Sintered body for forming low refractive index film and method of producing the same

The present invention relates to a sintered body for forming an amorphous and low refractive index film and a method for producing the same.

In recent years, research on softening has been carried out in the field of processing light such as a display, a solar cell, or a touch panel. When light is used in a display or the like, it is particularly preferable to have high transmittance in the entire region of the visible light region. Further, when the refractive index is high, the optical loss is increased or the viewing angle dependence of the display is deteriorated. Therefore, an amorphous film having a low refractive index or a film cracking or etching property is expected.

The amorphous film has a small stress and is less likely to be cracked than the crystal film. Therefore, it is considered that an amorphous film is required to be softened in the future.

For example, as a transparent conductive film, a film obtained by adding tin 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, the ITO must be crystallized to increase the low resistance value or the transmittance, and if it is in an amorphous state, it absorbs in a short-wavelength region and does not become a transparent film, so it is not suitable for soft use.

IZO (Indium-Zinc-Oxide), AZO (Aluminium-Zinc-Oxide), GZO (Gallium-Zinc-Oxide), and the like are known as other transparent conductive film materials (Patent Documents 1 to 3). However, although IZO can be made into a low-resistance amorphous film, it has a problem of absorption in a short-wavelength region.

Further, since AZO and GZO are c-axis alignment crystal films of ZnO, there are problems such as large stress, film peeling, or film breakage, and thus they are not suitable for soft use. Further, since the refractive indices of ITO, IZO, AZO, and GZO are both 2.0 or more, a material having a low refractive index and a high transmittance and being an amorphous film is required.

An object of the present invention is to provide a sintered body which can obtain a film having a low refractive index which can maintain a good visible light transmittance and a refractive index of 2.0 or less, and an amorphous film. Since the film has a high transmittance and a low refractive index and is an amorphous film, it is useful as a display, a solar cell, a transparent conductive film of a touch panel, or a protective layer.

Further, Patent Document 4 discloses a light-transmitting conductive material which has a wide refractive index by using ZnO and a fluorinated alkaline earth metal compound as main components. However, this is a crystallized film, and the effect of the amorphous film of the present invention described below cannot be obtained. Further, Patent Document 5 discloses a transparent conductive film having a small refractive index and a small specific resistance and further amorphous. However, the composition system is different from the present invention, and there is a problem that the refractive index and the resistance value cannot be adjusted together.

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

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

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

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

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

An object of the present invention is to provide a thin film which can maintain a good visible light transmittance (an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 or less (wavelength: 550 nm), and a sintered body of an amorphous film. . Since the film has a high transmittance and a low refractive index and is an amorphous film, it is useful as a display, a solar cell, a transparent conductive film of a touch panel, or a protective layer.

In order to solve the above problems, the inventors of the present invention conducted intensive studies, and as a result, obtained the following findings: by using zinc (Zn), magnesium (Mg), oxygen (O), fluorine (F) as a main component and magnesium (Mg) The content contains 1.0 to 27 mol% of the sintered body in terms of magnesium fluoride (MgF ₂ ), and can form a film which ensures the amorphous stability of the film after film formation and maintains good visible light transmission. The ratio (the extinction coefficient of 0.01 or less (wavelength: 450 nm)) and the refractive index of 2.0 or less (wavelength: 550 nm) have a low refractive index. Furthermore, the following insights are obtained: the implementation is less than 10Ω. The low bulk resistance of cm enables high-speed film formation by DC (direct current) sputtering, and ion plating and RF sputtering can be performed as needed.

Further, when a low refractive index film is formed by ion plating, if the evaporation raw material for ion plating is in accordance with the composition of the film, the evaporation raw material can be directly used for ion plating, so that it can be operated more easily. advantage. However, when the vapor pressure of the oxide added as the auxiliary component is significantly different from the zinc oxide (ZnO) which is the main component, if the film is formed by the ion plating method, the film having the same composition is not formed. Degree adjustment.

The present invention provides the following invention based on this finding.

1) A sintered body comprising zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 in terms of magnesium fluoride (MgF ₂ ) ~27mol%.

2) The sintered body according to the above 1), wherein the ratio of the peak intensity of the magnesium fluoride (MgF ₂ ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more.

(3) The sintered body according to the above 1) or 2) further comprising, in an amount of 0.2 to 10 mol%, in terms of an oxide of each element, selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), and indium (In). One or more elements of tin (Sn).

The sintered body according to any one of the above 1 to 3, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight.

5) The sintered body according to the above 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 , An oxide of one or more of the group consisting of Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , and MoO ₃ .

6) The sintered body according to any one of the above 1) to 5), which has a relative density of 90% or more.

7) The sintered body according to any one of the above 1) to 6), which has a bulk resistance of less than 10 Ω. Cm.

8) The sintered body according to any one of the above 1) to 7) which is a sputtering target or a material for ion plating.

9) A film comprising zinc (Zn), magnesium (Mg), oxygen (O), fluorine (F), characterized in that the content of magnesium (Mg) is 1.0% in terms of magnesium fluoride (MgF ₂ ). 27 mol%.

10) The film according to the above 9), which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) in terms of oxide of each element. One or more elements.

11) The film according to the above 9) or 10) further containing 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight.

12) The film according to the above 11), 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 , Ti An oxide of one or more of ₂ O ₃ , PbO, Bi ₂ O ₃ , and MoO ₃ .

13) The film according to any one of the above 9) to 12) which is amorphous.

14) The film according to any one of the above 9) to 13), which has a refractive index of 2.0 or less (wavelength: 550 nm).

15) The film according to any one of the above 9) to 14), which has an extinction coefficient of 0.01 or less (wavelength: 450 nm).

The film according to any one of the above 9), wherein the film has a resistance value of from 1 × 10 ^-3 to 1 × 10 ⁹ Ω. Cm.

17) The film according to any one of the above 9) to 16) which is formed by sputtering or ion plating.

18) A method for producing a sintered body for producing the sintered body according to any one of the above 1) to 5) which is sintered in an inert atmosphere.

(19) A method for producing a material for ion plating, which comprises pulverizing the sintered body according to any one of the above 1) to 5) to obtain a powder or a pellet.

According to the above, zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F) are contained as main components, and magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF ₂ ). The sintered body of % has an excellent effect of forming a low refractive index amorphous film having a good visible light transmittance (having an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 or less (wavelength: 550 nm). Furthermore, the implementation is less than 10Ω. The low bulk resistance of cm enables high-speed film formation by DC (direct current) sputtering, and ion plating and RF sputtering can be performed as needed.

Further, in the case of ion plating, it is possible to avoid the problem that the evaporation rate of the oxide added as the subcomponent is significantly different from the zinc oxide (ZnO) which is a main component. Therefore, as a result, it is possible to form and ion plating. A film having substantially the same composition as the raw material is used, and the film can be formed at a high speed.

Fig. 1 is a graph showing the results of measurement of the ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity).

Fig. 2 is a graph showing vapor pressure curves of respective oxides and fluorides in comparison with ZnO.

Fig. 3 is a graph showing vapor pressure curves of oxides of Al ₂ O ₃ , MgO, and SiO _{2 in} comparison with ZnO.

The sintered body of the present invention is composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), and is characterized in that the content of magnesium (Mg) is 1.0% in terms of magnesium fluoride (MgF ₂ ). 27 mol%.

Further, one of the characteristics of the sintered body of the present invention is that the ratio of the peak intensity of the magnesium fluoride (MgF ₂ ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more.

Further, the sintered body of the present invention may contain, in an amount of 0.2 to 10 mol%, in terms of an oxide of each element, selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn). Kind of above elements.

Further, the sintered body of the present invention may contain 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. 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 , Ti ₂ O ₃ , PbO, and Bi _{2 .} One or more oxides of the group of O ₃ and MoO ₃ may be used.

The above added elements (oxides) can be arbitrarily selected, and the characteristics depending on the respective added elements can be improved. These sintered systems are useful as a sputtering target and further as an ion plating material. Hereinafter, the case where the sintered body of the present invention is applied will be described in detail.

The sintered body of the present invention is composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), and the magnesium (Mg) content is 1.0 to 27 mol% in terms of magnesium fluoride (MgF ₂ ).

In the case of adjusting the raw material, the ratio of each oxide and fluoride is adjusted so as to have a total composition of 100 mol%, and the remaining portion is ZnO, but the Zn content can be obtained from the remaining portion of ZnO. By adopting such a composition, an amorphous film having a good transmittance of visible light and a low refractive index can be produced, whereby the above effects of the present invention can be obtained.

In the present invention, the content of each metal in the sintered body is determined in terms of oxide conversion or fluoride conversion, but one part of each metal in the sintered body exists as a composite oxide. Moreover, in the component analysis of the sintered body which is generally used, the content of each is measured not in the form of a metal but not an oxide or a fluoride. Therefore, each composition range is obtained by converting the analysis value of each metal in the sintered body into the amount of each oxide and fluoride.

The magnesium fluoride is effective for amorphization and low refractive index of the film. If it is less than 1.0 mol%, there is no effect of addition, and if it exceeds 27 mol%, the problem of high resistivity of the film occurs, so the above numerical range is set.

The presence of magnesium fluoride (MgF ₂ ) in the sintered body can be confirmed by X-ray diffraction. That is, the ratio of the peak intensity of the magnesium fluoride (MgF ₂ ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is set to 1.50 or more.

In the measurement of the peak intensity of MgF ₂ , the produced sputtering target or the powder which pulverized the sputtering target was measured by an X-ray diffraction method. Namely, the intensity in the vicinity of 2θ: 27.3° at which the peak of the (110) plane of MgF ₂ appeared was measured, and the background intensity (the average of the intensities of 28.0 to 29.0 °) was measured.

Thereby, the ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was determined. For this purpose, Ultimal V manufactured by Rigaku Corporation can be used as the measuring device.

As described above, as an element to be further added, one or more elements selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) may be contained in an amount of 0.2 to 10 at. % of these elements. Conductivity can be imparted by adding an oxide of 0.2 to 10 mol% of these elements in terms of element amount.

When the amount of the oxide of the element is less than 0.2 mol% in terms of the amount of the element, the effect is small, and when it exceeds 10 mol%, the effect is saturated. Therefore, it is most preferable to set it as the above range.

Further, niobium oxide and boride oxide are also oxides formed on glass, and are effective for amorphization and low refractive index of the film. When it is less than 0.2 mol% in terms of element amount, there is no effect of addition, and if it exceeds 10 mol%, there arises a problem that the film has high resistivity, and thus it is set to the above numerical range.

Further, it is effective that the sintered body of the present invention contains a metal which forms an oxide (low melting point oxide) having a melting point of 1000 ° C or less. Zinc oxide (ZnO) is more easily reduced and evaporated, so that the sintering temperature may not be increased to such an extent that it is difficult to increase the density of the sintered body. However, by adding such a low-melting-point oxide, the effect of increasing the density can be achieved by increasing the sintering temperature to such an extent.

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 . The oxides may be separately added and compounded separately, and may achieve the object of the invention.

The metal forming the above-mentioned low melting point oxide preferably contains 0.1 to 5 wt% in terms of weight of the oxide. If it is less than 0.1% by weight, the effect cannot be sufficiently exerted, 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 set to 90% or more. Preferably, the relative density is 92% or more, and the relative density is 99% or more. The present invention achieves such a high density target.

The increase in density has an effect of improving the uniformity of the sputtering film and suppressing the generation of particles at the time of sputtering.

This sintering system is used to industrially produce a film having a particularly good transmittance of visible light (having an extinction coefficient of 0.01 or less (wavelength: 450 nm)) and a refractive index of 2.0 (wavelength of 550 nm) or less. Further, the above extinction coefficient can be made to be <0.005 (wavelength: 450 nm). Such a good transmittance of visible light and a film having a low refractive index are particularly useful as a film for a protective display, an organic EL television, an electrode for a touch panel, and a protective layer for an optical information recording medium.

In the present invention, zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F) are used as main components, and magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF ₂ ). The film formed of the sintered body of % ensures the amorphous stability of the film, and further forms a film capable of maintaining good transmittance of visible light (extinction coefficient of 0.01 or less (wavelength: 450 nm)) and refractive index of 2.0 or less (wavelength of 550 nm). ) low refractive index.

The sintered body of the present invention can be produced by subjecting a powder of each constituent element having an average particle diameter of 5 μm or less to atmospheric pressure sintering or high-temperature pressure sintering in an inert atmosphere.

Further, by using the sintered body of the present invention, it is possible to obtain a material having improved productivity and excellent quality, and it is possible to stably produce a good transmittance of visible light at a low cost (with an extinction coefficient of 0.01 or less). A low refractive index film (wavelength: 450 nm) and a refractive index of 2.0 or less (wavelength: 550 nm).

Further, the sintered body is achieved to be less than 10 Ω. Low body resistance of cm, and high-speed film formation by DC (direct current) sputtering. Moreover, the DC sputtering apparatus has the advantages of being inexpensive, easy to control, and having a small amount of power consumption. Further, in the present invention, depending on the production conditions and material selection, it is necessary to perform ion plating or RF sputtering, but even in this case, the film formation speed is improved.

Next, a case where the sintered body of the present invention is used for ion plating will be described. In the material for ion plating for forming a low refractive index film of the present invention, oxidation of one or more elements selected from the group consisting of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (Sn) The materials (Ga ₂ O ₃ , B ₂ O ₃ , GeO ₂ , In ₂ O ₃ , SnO ₂ ) and magnesium fluoride (MgF ₂ ) have a vapor pressure similar to that of zinc oxide, so that they can be used for ion plating without problems. material. The vapor pressure curves of the respective oxides and fluorides in comparison with ZnO are shown in Fig. 1.

For comparison, the vapor pressure curves of the oxides of Al ₂ O ₃ , MgO, and SiO _{2 in} comparison with ZnO are shown in FIG. As is clear from Fig. 2 and Fig. 3, the oxide system shown in Fig. 3 has a large difference in vapor pressure as compared with ZnO.

The Al shown in FIG. ₂ 2 O _3, MgO, SiO ₂ oxide added to the ZnO as a target by sputtering, but there is a big different on the vapor pressure, therefore, may be considered somewhat unsuitable as ion plating with material. For such a material, a target for sputtering can be produced and used.

When a material for ion plating is produced, a raw material powder of magnesium fluoride (MgF ₂ ) is added to zinc oxide (ZnO) which is a main component, or zinc oxide (ZnO) which is a main component is added to gallium (Ga). An oxide of one or more elements of boron (B), germanium (Ge), indium (In), and tin (Sn) (Ga ₂ O ₃ , B ₂ O ₃ , GeO ₂ , In ₂ O ₃ , SnO ₂ The raw material powder is preliminarily mixed, sintered, and integrated to form a sintered body, which is further pulverized to obtain a powder or a granule, thereby being used for a material for ion plating.

The composition of the material of the ion plating can be arbitrarily adjusted according to the purpose of film formation. For example, it can be used for flexible displays, organic EL televisions, electrodes for touch panels, and formation of light resources. The protective layer of the recording medium. As described above, since there is no large change in the vapor pressure, the composition of the ion plating material can be reflected as the composition of the low refractive index film. Therefore, it is possible to form a film at a high speed, and it is possible to have stable amorphous properties and excellent transmittance.

Example

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

(Example 1)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, and 3N equivalents of GeO ₂ powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF ₂ powder and the GeO ₂ powder are blended into a blend ratio of ZnO:MgF ₂ :GeO ₂ =85.0:13.6:1.4 mol%, and after mixing, at 900 ° C, Ar environment, 250 kgf The powder material was subjected to hot press sintering under a pressure of /cm ² . The sintered body is finally processed into a target shape by mechanical processing.

As a result of the above, the relative density of the sputtering target of Example 1 was 92.0%, and the bulk resistance value was 1.2 Ω. Cm, and stable DC sputtering can be performed. The film formation rate was 2.6 Å/sec, and the film formation speed was good. The refractive index was 1.90 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 ⁶ Ω. Cm, the extinction coefficient (γ = 450 nm) becomes <0.005.

The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 19.5. This result is shown in FIG.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Example 2)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, and 3N equivalents of GeO ₂ powder having an average particle diameter of 5 μm or less were prepared. Then, ZnO powder, MgF ₂ powder and GeO ₂ powder were blended into a blend ratio of ZnO:MgF ₂ :GeO ₂ =82.0:9.8:8.2 mol%, and after mixing, the powder material was taken at 800 ° C in the atmosphere. Hot press sintering is performed. The sintered body was pulverized and formed into a granular body having a particle diameter of 1 to 6 mm to prepare an ion plating material.

Then, ion plating was carried out using the ion plating material. As a result, it was confirmed that, as in the following Comparative Example 1, no evaporation residue was observed in the crucible, and there was almost no vapor pressure difference between ZnO and MgF ₂ and GeO ₂ during ion plating. The difference caused. The ion plating material of Example 2 was subjected to stable ion plating, and the transmittance of the film produced was 86.6% (405 nm), and the refractive index was 1.92, showing amorphousness. Moreover, the specific resistance value becomes 1 × 10 ⁵ Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

The peak intensity of MgF ₂ was obtained by pulverizing the obtained ion plating material by a powder X-ray diffraction method. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 16.3. This result is shown in FIG.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Example 3)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, 3N equivalents of GeO ₂ powder having an average particle diameter of 5 μm or less, and 3 N equivalents of Ga _{2 having} an average particle diameter of 5 μm or less. O ₃ powder. Then, ZnO powder, MgF ₂ powder, Ga ₂ O ₃ powder and GeO ₂ powder are conditioned to a blend ratio of ZnO:MgF ₂ :Ga ₂ O ₃ :GeO ₂ =73.5:16.8:4.1:5.6 mol%, and After the mixing, the powder material was subjected to hot press sintering at a pressure of 250 kgf/cm ² at 1,100 ° C in an Ar environment. The sintered body is finally processed into a target shape by mechanical processing.

As a result of the above, the relative density of the sputtering target of Example 3 was 99.6%, and the bulk resistance value was 4 × 10 ^-3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.84 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 ^-1 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 24.1.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Example 4)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, and 3N equivalents of SnO ₂ powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF ₂ powder and the SnO ₂ powder are adjusted into a blend ratio of ZnO:MgF ₂ :SnO ₂ powder=83.5:8.1:4.1:8.4 mol%, and after mixing, at 1050 ° C, Ar environment The powder material was subjected to hot press sintering at a pressure of 250 kgf/cm ² . The sintered body is finally processed into a target shape by mechanical processing.

As a result of the above, the relative density of the sputtering target of Example 4 was 99.2%, and the bulk resistance value was 6 × 10 ^-3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.96 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 ^-2 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes 0.008. The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 14.2.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Example 5)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, ₃ N equivalents of In ₂ O ₃ powder having an average particle diameter of 5 μm or less, and ₃ N equivalents and an average particle diameter of 5 μm or less. GeO ₂ powder. Then, ZnO powder, MgF ₂ powder, In ₂ O ₃ powder and GeO ₂ powder are conditioned to a blend ratio of ZnO:MgF ₂ :In ₂ O ₃ :GeO ₂ =83.9:6.1:2.77:7.2 mol%, and After mixing, the powder material was subjected to hot press sintering at a pressure of 250 kgf/cm ² at 1050 ° C in an Ar environment. The sintered body is finally processed into a target shape by mechanical processing.

As a result of the above, the relative density of the sputtering target of Example 5 was 99.3%, and the bulk resistance value was 3 × 10 ^-3 Ω. Cm, and stable DC sputtering can be performed. The refractive index was 1.93 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes 1 × 10 ^-1 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 9.8.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Comparative Example 1)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less and 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder and the MgF ₂ powder are blended into a blend ratio of ZnO:MgF ₂ =99.2:0.8 mol%, and after mixing, the powder material is pressed at 1100 ° C, Ar environment, under a pressure of 250 kgf / cm ² Hot press sintering is performed. The sintered body is finally processed into a target shape by mechanical processing. The amount of MgF ₂ did not reach the amount set as the object of the present invention.

As a result of the above, the relative density of the sputtering target of Comparative Example 1 was 98.0%, and the bulk resistance value was 2 × 10 ^-3 Ω. Cm, and stable DC sputtering can be performed. The refractive index of 2.01 (wavelength 633 nm) was insufficient, and no amorphous property was shown. Moreover, the specific resistance value becomes 1 × 10 ^-2 Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 1.7.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

(Comparative Example 2)

3N equivalents of ZnO powder having an average particle diameter of 5 μm or less, 3N equivalents of MgF ₂ powder having an average particle diameter of 5 μm or less, and 3 N equivalents of Ga ₂ O ₃ powder having an average particle diameter of 5 μm or less were prepared. Then, the ZnO powder, the MgF ₂ powder and the Ga ₂ O ₃ powder are conditioned to a blend ratio of ZnO:MgF ₂ :Ga ₂ O ₃ =69.2:29.0:1.8 mol%, and after mixing, at 1050 ° C, Ar The powder material is subjected to hot press sintering in an environment at a pressure of 250 kgf/cm ² . The sintered body is finally processed into a target shape by mechanical processing.

As a result of the above, the relative density of the sputtering target of Comparative Example 2 was 97.6%, and the bulk resistance value was >10 Ω. Cm, and stable DC sputtering is not possible. The refractive index was 1.78 (wavelength: 633 nm) and showed amorphous properties. Moreover, the specific resistance value becomes >1 × 10 ⁹ Ω. Cm, the extinction coefficient (λ = 450 nm) becomes <0.005. The results are shown in Tables 1 and 2.

The XRD peak intensity of MgF ₂ was obtained by pulverizing the obtained sputtering target and measuring by powder X-ray diffraction. That is, the peak intensity appearing in the vicinity of 2θ: 27.3° was 553, and the background intensity (the average of the intensities of 28.0 to 29.0°) was measured.

The ratio of the peak intensity of MgF ₂ to the background intensity (MgF ₂ peak intensity/background intensity) was 36.4. This result is shown in FIG.

Further, Ulmital V manufactured by Rigaku Co., Ltd. was used as a measuring device, and the measurement conditions were a tube voltage of 40 kV, a tube current of 30 mA, a scanning speed of 8°/min, and a step angle of 0.02°.

[Industrial availability]

The film formed by using the sintered body of the present invention can provide a sintered body capable of obtaining a film having a low refractive index of a visible light having a good extinction coefficient of 0.01 or less (wavelength: 450 nm) and a refractive index of 2.0 or less. Further, an amorphous film. The film has a high transmittance, a low refractive index, and is an amorphous film, so as a display or a solar cell, a touch surface Useful for a transparent conductive film or a protective layer of a board. For example, it can be used for a flexible display, an organic EL television, an electrode for a touch panel, and a protective layer for forming an optical information recording medium.

Further, the present invention is characterized in that the target resistance value is reduced, the conductivity is imparted, and stable DC sputtering can be performed depending on the material. Further, it has a remarkable effect of making the controllability of sputtering easy to improve the film formation speed and improving the sputtering efficiency as a feature of the DC sputtering. Although ion plating or RF sputtering is performed as needed, in this case, an increase in film formation speed can also be seen.

As described above, it is possible to produce a film having a low refractive index which can maintain a good transmittance of visible light and a refractive index of 2.0 or less at a low cost and stably.

Claims (19)

A sintered body composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 to 27 mol in terms of magnesium fluoride (MgF ₂ ) %. The sintered body of the first aspect of the invention, wherein the ratio of the peak intensity of the magnesium fluoride (MgF ₂ ) to the background intensity (magnesium fluoride peak intensity/background intensity) in the X-ray diffraction is 1.50 or more. The sintered body according to claim 1 or 2, which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In) in terms of oxide of each element. One or more elements of tin (Sn). The sintered body according to any one of claims 1 to 3, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. 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 of Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , and MoO ₃ . The sintered body according to any one of claims 1 to 5, which has a relative density of 90% or more. The sintered body of any one of the claims 1 to 6 has a bulk resistance of less than 10 Ω. Cm. The sintered body according to any one of claims 1 to 7, which is a sputtering target or a material for ion plating. A film composed of zinc (Zn), magnesium (Mg), oxygen (O), and fluorine (F), characterized in that magnesium (Mg) content is 1.0 to 27 mol% in terms of magnesium fluoride (MgF ₂ ) . The film of claim 9 which further contains 0.2 to 10 mol% of gallium (Ga), boron (B), germanium (Ge), indium (In), and tin (in terms of oxide of each element). One or more elements of Sn). The film of claim 9 or 10, further comprising 0.1 to 5 wt% of a metal having an oxide having a melting point of 1000 ° C or less in terms of oxide weight. The film of claim 11, 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 of Ti ₂ O ₃ , PbO, Bi ₂ O ₃ , and MoO ₃ . A film according to any one of claims 9 to 12 which is an amorphous film. The film of any one of claims 9 to 13 has a refractive index of 2.0 or less (wavelength 550 nm). The film of any one of claims 9 to 14 has an extinction coefficient of 0.01 or less (wavelength: 450 nm). The film of any one of claims 9 to 15, wherein the film has a resistance value of from 1 × 10 ^-3 to 1 × 10 ⁹ Ω. Cm. The film of any one of claims 9 to 16, which is a film formed by sputtering or ion plating. A method of producing a sintered body for producing a sintered body according to any one of claims 1 to 5, which is sintered in an inert environment. A method for producing a material for ion plating, which is obtained by pulverizing a sintered body according to any one of claims 1 to 5 to obtain a powder or a pellet.