KR100814321B1 - Oxide sintered body and preparation process thereof, sputtering target and transparent electroconductive films - Google Patents

Abstract

[assignment]

When used as a sputtering target, an oxide sintered body, a method for producing a small transparent conductive film of Ra or Ry, which can be used for organic EL, high-definition LCD, and the like, can be obtained from the beginning to the end of use, and a sputtering target and A transparent conductive film is provided.

[Resolution]

An oxide sintered body containing indium oxide and tin oxide as necessary and silicon oxide, and having a relative density of 102% or more.

Sputtering, target, discharge, Ra, Ry, transparent conductive film, oxide sintered body, indium oxide, tin oxide, silicon oxide.

Description

OXIDE SINTERED BODY AND PREPARATION PROCESS THEREOF, SPUTTERING TARGET AND TRANSPARENT ELECTROCONDUCTIVE FILMS}

1 is a photograph showing an SEM image of Example 1. FIG.

2 is a photograph showing an SEM image of Example 2. FIG.

3 is a photograph showing an SEM image of Comparative Example 2. FIG.

4 is a photograph showing an SEM image of Comparative Example 5. FIG.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxide sintered body that can be used for sputtering targets and tablets used in the sputtering method and the ion plating method for forming a transparent conductive film, a method for producing the same, and a sputtering target using the same, in particular, an LCD (liquid crystal display) or organic It is usefully used for forming a transparent electrode of a flat-panel display (FPD) such as an EL display.

Indium oxide-tin oxide (composite oxide of In ₂ O ₃ -SnO ₂ , hereinafter referred to as "IT0") film has high visible light transmittance and high conductivity, and thus generates heat for preventing condensation of a liquid crystal display or glass as a transparent conductive film. It is widely used in films, infrared reflecting films and the like. For example, as for the transparent conductive film used for flat panel display FPD, the thing of low resistance (resistance of about 2x10 <^{-4> (} ohm) * cm) is selected.

Under such a situation, a transparent conductive film having indium oxide as a main component and doped with tin oxide, silicon oxide and / or aluminum oxide is proposed as having high resistance and good transparency (see Patent Document 1).

However, according to the example of this publication, the sputtering target which forms a transparent conductive film is not a sintered compact but a green compact, high resistance, and a DC magnetron cannot be used.

On the other hand, the present applicant first has a bulk resistance enough to be used in a DC magnetron sputtering apparatus, but the transparent conductive film formed is a high resistance and high light transmittance sputtering target. The sputtering target for resistance transparent conductive films was developed (refer patent document 2). Moreover, the sputtering target which has indium oxide and tin oxide as a main component and contains at least one of silicon oxide or titanium oxide is disclosed (refer patent document 3). Moreover, the technique of forming a low-resistance transparent conductive film by the sputtering target containing silicon oxide but not having the silicon oxide phase of a high resistance material is also proposed (refer patent document 4).

However, subsequent studies have shown a problem that if the sputter discharge is continued for a long time, it is because an insulating layer such as silicon oxide is present or abnormal discharge is likely to occur, and stable sputter discharge cannot be maintained until the end.

For example, the technique described in Patent Literature 3 is the addition of silicon oxide, which is an insulator for the purpose of high resistance, so that an insulator made of silicon oxide exists inside the sintered body, and abnormal discharge due to dielectric breakdown caused by charged charges exists. There exists a problem that sputter discharge which is a cause for a long time and is not obtained for a long time is obtained. Moreover, there also exists a problem that particle | grains generate | occur | produce by abnormal discharge, and productivity of a device etc. falls. Moreover, the sintered compact described in the Example of patent document 4 also contains many pinholes at low density, and there exists a problem that an abnormal discharge is easy to produce over a long term.

Moreover, the target which added silicon oxide to ITO conventionally became the amorphous transparent conductive film formed by sputtering using it, and the residue by wet etching became favorable compared with ITO, but it was still inadequate.

In addition, the transparent conductive film formed of such a conventional sputtering target does not have good surface smoothness, and there is a problem that there is a possibility that adverse effects on the display device may occur due to overcurrent to the sharp portion. In particular, in surface smoothness, when the maximum height difference Ry is large, there exists a problem that it becomes easy to become a starting point of an overcurrent.

The surface smoothness of this transparent conductive film is an important film characteristic especially in the field of organic EL, and is a film characteristic for LCD realized in the ITO film used for LCD, for example, surface smoothness of Ra = 0.74 nm and Ry = 11.3 nm. In this case, the film characteristics for organic EL cannot be satisfied.

In the LCD, although the surface smoothness of the developed ITO film is sufficient, when Ra and Ry become small, the etching residue decreases and pattern processing by highly precise wet etching becomes possible.

Therefore, the emergence of the small transparent conductive film of Ra and Ry used for organic electroluminescent, high-definition LCD, etc., and the sputtering target which can implement | achieve it are desired.

[Patent Document 1] Japanese Patent Application Laid-Open No. 4-206403 (Configuration of the Invention, etc.)

[Patent Document 2] Japanese Unexamined Patent Publication No. 2003-105532 (Configuration of the Invention, etc.)

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-277921 (Patent Claims, etc.)

[Patent Document 4] Japanese Patent Application Laid-Open No. 2004-123479 (Embodiment of the Invention, etc.)

In view of the above circumstances, the present invention, when used as a sputtering target, an oxide capable of achieving stable sputter discharge from the beginning to the end of use and realizing a small Ra or Ry used for organic EL, high definition LCD, or the like. It is a problem to provide a sintered compact, its manufacturing method, a sputtering target, and a transparent conductive film.

The 1st aspect of this invention which solves the said subject is an oxide sintered compact containing indium oxide and tin oxide as needed, and a silicon oxide, Comprising: It exists in the oxide sintered compact characterized by the relative density being 102% or more.

In such a first aspect, by using an oxide sintered body having a relative density of 102% or more, for example, when using a sputtering target, a stable sputter discharge is obtained from the beginning to the end of use, and a transparent conductive film having a smooth surface is obtained. .

According to a second aspect of the present invention, in the oxide sintered body according to the first aspect, the number of pinholes having a Feret diameter (microscope method; forward tangential diameter) of 2 µm or more in the sintered body is 50 pieces / mm ² or less per unit area. In the oxide sintered body.

In this 2nd aspect, since the pinhole number in a sintered compact is small, when a sputtering target is used, for example, abnormal discharge hardly occurs.

According to a third aspect of the present invention, in the oxide sintered body according to the first or second aspect, the ratio of the precipitated phase when the microscope observes any cross section of the sintered body is 40% or more by area ratio. .

In this 3rd aspect, since the ratio of a precipitated phase is 40% or more, for example, when it is set as a sputtering target, the film | membrane whose characteristic is stable until the end of use can be obtained.

According to a fourth aspect of the present invention, in the method for producing an oxide sintered body containing indium oxide and tin oxide as necessary and containing silicon oxide, the raw material of the silicon oxide raw material powder is 0.2 m to 0.6 m, and the other raw material is used. After mixing with powder, it sintered at baking temperature 1400 degreeC or more, The manufacturing method of the oxide sintered compact characterized by the above-mentioned.

In this fourth aspect, since the silicon oxide raw material powder is sintered by having a predetermined particle diameter, the sintered density of the sintered compact is remarkably improved. For example, when the sputtering target is used, stable sputter discharge is obtained from the beginning to the end of use. Furthermore, the oxide sintered compact from which the transparent conductive film with a smooth surface is obtained is obtained.

5th aspect of this invention is the manufacturing method of the oxide sintered compact in the manufacturing method of the oxide sintered compact of 4th aspect WHEREIN: The relative density of the obtained oxide sintered compact is 102% or more.

In this fifth aspect, an oxide sintered body having a relative density of 102% or more is obtained. For example, when using a sputtering target, a stable sputter discharge is obtained from the beginning to the end of use, and a transparent conductive film having a smooth surface is obtained. Obtained.

The 6th aspect of this invention bonded the oxide sintered compact as described in any one of 1st-3 to the backing plate, The sputtering target characterized by the above-mentioned.

In this sixth aspect, when using a sputtering target, stable sputter discharge is obtained from the beginning to the end of use.

According to a seventh aspect of the present invention, in the sputtering target according to the sixth aspect, the maximum smoothness (Ry) of the surface smoothness of the transparent conductive film formed on the glass substrate by sputtering at a thickness of 200 nm is 6.0 nm or less. Is in the sputtering target.

In this seventh aspect, a transparent conductive film having a maximum height difference Ry of 6.0 nm or less is obtained, and generation of overcurrent is prevented.

An eighth aspect of the present invention is a transparent conductive film formed by sputtering using the sputtering target according to the sixth or seventh aspect, wherein the surface smoothness of the transparent conductive film formed on the glass substrate at a film thickness of 200 nm by sputtering, The maximum height difference Ry is 6.0 nm or less, It is a transparent conductive film characterized by the above-mentioned.

In this eighth aspect, the maximum height difference Ry becomes a transparent conductive film of 6.0 nm or less, and generation of overcurrent is prevented.

Best Mode for Carrying Out the Invention

The oxide sintered body according to the present invention is an oxide sintered body containing indium oxide and tin oxide as required and at the same time silicon oxide, characterized in that the relative density is 102% or more, for example, when used as a sputtering target It is said that stable sputter discharge is obtained from the beginning to the end.

Here, stable sputter discharge means that abnormal discharge does not occur as much as possible, and that cracks, residues or cracks of particles and targets do not occur, and that the characteristics of the sputter film formed by sputtering have a small change over time from the beginning to the end of use. Say that.

Thus, the oxide sintered body whose relative density is 102% or more improves mechanical strength, it is hard to produce a crack and a crack, and stable sputter discharge is obtained. Moreover, when sputter | spattering such an oxide sintered compact, the sputter film obtained has the advantage that the surface is very smooth.

When the relative density is less than 102%, the mechanical strength is low at 102% or more, so that cracks and cracks are likely to occur, and the surface smoothness of the sputtered film tends to be deteriorated.

Here, smoothness means that the maximum height difference Ry of surface smoothness is 10.0 nm or less, Preferably it is 6.0 nm or less. Thus, as the maximum height difference (Ry) becomes 10.0 nm or less, preferably 6.0 nm or less, smoothness can be prevented, and overcurrent to the sharp part of the sputter film can be prevented, and overcurrent to the organic EL display element due to the overcurrent to the sharp part Adverse effects can be excluded. Moreover, the residue by wet etching in the manufacturing process of high definition LCD can be reduced.

The relative density is a density calculated relative to the theoretical density. An example of calculation of theoretical density is shown. The density of each raw material In ₂ O ₃ is 7.179 g / cm ³ , the density of SnO ₂ is 6.950 g / cm ³ , the density of SiO ₂ is 2.200 g / cm ³ , and the density calculated from the weighted average is the theoretical density. Let this be 100%. For example, the theoretical density of 85 wt% In ₂ O ₃ -10 wt% SnO ₂ -5 wt% SiO ₂ is 6.43 g / cm ³ , and the actual density of 100% relative density in the composition is 6.43 g / cm ³ .

In this case, the oxide sintered body having a relatively high relative density has a small pinhole number and is unlikely to cause abnormal discharge. However, in a preferable case, the number of pinholes having a Feret diameter of 2 µm or more in the sintered body is 50 pieces / mm ² per unit area. It becomes as follows. As described above, when the number of the pinholes having a Feret diameter of 2 µm or more in the sintered body is 50 / mm ² or less, abnormal discharge can be suppressed from the beginning to the end of the target use, and the sputter film obtained is very smooth.

In addition, when the number of pinholes having a Feret diameter of 2 µm or more in the sintered body is larger than 50 / mm ² , a large number of abnormal discharges tend to occur from the beginning to the end of the target use, which is not preferable, and the smoothness of the resulting sputtered film also decreases. have.

Here, a Feret diameter means the parallel space | interval of the predetermined direction which interposes particle | grains, when a pinhole is compared as particle | grains. For example, it can measure by observation by SEM image of 100 times magnification. Specifically, an arbitrary fracture surface of the sintered compact is polished until it becomes a mirror surface state, and the pinhole is specified by binarizing a SEM image with a magnification of 100 times, thereby obtaining image processing software (particle analysis III: manufactured by AI Soft Co., Ltd.). By this, the pinhole number of 2 micrometers or more of Feret diameter was counted.

Moreover, in the oxide sintered compact of this invention, when it is preferable, the ratio of the precipitated phase at the time of microscopic observation of the arbitrary cross section of the said sintered compact is 40% or more by area ratio. Thus, when the precipitated phase becomes 40% or more, for example, when the sputtering target is used, the sputtering film becomes stable in the end of the target use from the beginning, and the sputtering film tends to be smoother.

In addition, when the ratio of the precipitated phase is less than 40% by area ratio, when used as the sputtering target, the characteristics of the sputtered film tend to be greatly changed from the beginning of the target use to the end, which is not preferable, and the smoothness of the sputtered film is lowered. It becomes a tendency.

Here, the precipitated phase is precipitated as a crystal phase inside the oxide sintered body and can be detected by microscopic observation of an arbitrary cross section. For example, it can detect by SEM image of 5000 times magnification. In this invention, the area ratio of the precipitation phase in arbitrary cross section is prescribed | regulated and 40% or more is said to be preferable.

Specifically, in order to obtain an arbitrary cross section, the fracture surface is polished until it becomes a mirror state, and further etched with an acid, and then the cross section is observed, for example, by observing an SEM image with a magnification of 5000 times. Can be calculated. In addition, this precipitated phase is considered to be an In ₂ Si ₂ O ₇ phase as a result of X-ray diffraction, as will be described later.

Tin oxide (Sn) is contained in the oxide sintered compact of this invention as needed. When tin is contained, it is preferable to contain 0.001-0.3 mol, preferably 0.01-0.15 mol, More preferably, 0.05-0.1 mol with respect to 1 mol of indium. If it is in this range, the density and mobility of the carrier electrons of a sputtering target can be suitably controlled, and electroconductivity can be maintained in a favorable range. Moreover, when it adds exceeding this range, since it reduces the mobility of the carrier electron of a sputtering target, and works in the direction which degrades electroconductivity, it is unpreferable.

The manufacturing method of the oxide sintered compact of this invention is demonstrated below.

In general, powders of In ₂ O ₃ , SnO ₂ , and SiO ₂ are used as starting materials constituting the oxide sintered body, but these single particles, compounds, composite oxides, and the like may be used as raw materials. In the case of using a single element or a compound, an oxide process is carried out in advance. In addition, it is important here that the average particle diameter of a silicon oxide raw material powder shall be 0.2 micrometer-0.6 micrometer.

That is, in the preferred method for producing the oxide sintered body of the present invention, in the method for producing an oxide sintered body containing indium oxide and tin oxide as necessary and containing silicon oxide, the average particle diameter of the silicon oxide raw material powder is 0.2 µm to It is said to sinter at baking temperature 1400 degreeC or more after mixing with another raw material powder as 0.6 micrometer. More specifically, first, in the method for producing an oxide sintered body containing indium oxide and, if necessary, preferably 5 to 15 wt% tin oxide, and preferably 2 to 8 wt% silicon oxide, oxidation After mixing the raw material powder with the average particle diameter of 0.2 micrometer-0.6 micrometer for 5 to 48 hours by the other raw material powder with a dry ball mill, the # 1500 PVA binder is 3-8 wt% with respect to the weight of the mixed powder to the obtained mixed powder. Add and mix by induction or the like. After sorting this with a 20-30 mesh sieve etc., it is filled uniformly in a metal mold | die and press-molded by the pressure of 500 kg / cm <^2> -5 ton / cm < ² > by a cold press method. If it is less than 500 kg / cm <^2>, shaping | molding density will fall, progress of sintering will become inadequate, and sintering density will fall. If it is larger than 5 ton / cm ² , the installation is large and undesirable. The molded body is air-fired at a firing temperature of 1400 ° C. or higher. For temperature rise, the temperature is raised to 40 to 100 ° C./hr from room temperature to 800 ° C., in order to make the temperature distribution in the fired body uniform. Therefore, the temperature is maintained at 800 ° C. for 4 hours or more, the temperature is increased to 50 to 450 ° C./hr up to 800 to 1300 ° C., and the temperature is increased to 50 to 100 ° C./hr up to 1300 ° C. to the set temperature (for example, 1450 ° C.). Maintain at least 4 hours at temperature. About temperature reduction, it cools to 50-400 degreeC / hr to room temperature.

In this manner, the average particle diameter of the silicon oxide raw material powder is 0.2 to 0.6 µm and the firing temperature is 1400 ° C or more, whereby the density of the oxide sintered body is remarkably improved, the pinholes in the sintered body are reduced, and the precipitated phase can be increased. have.

In addition, when the average particle diameter of the silicon oxide raw material powder is smaller than 0.2 µm, in particular, when the average particle diameter is 0.05 µm or less, the density after firing decreases, which is undesirable, and when the average particle diameter is larger than 0.6 µm, the sintered density decreases or precipitates. It is not preferable because the phase is reduced.

Here, although the particle diameter of raw material powders other than a silicon oxide raw material is not specifically limited, The thing of about 0.3-1.5 micrometers in average particle diameter, Preferably the thing of about 0.4-1.1 micrometers can be used.

The sintering temperature is preferably 1400 ° C. or higher because the relative density is improved, and the smoothness of the sputtered film is improved. However, in order to further improve the relative density and to reduce the warpage of the sintered body by firing, it is 1450 ° C. to 1550 ° C. It is more preferable to set it as. Moreover, even if it exceeds 1550 degreeC and especially bakes at 1600 degreeC or more, the improvement of an effect is not remarkable, The installation cost and running cost of a kiln become expensive, and it becomes an undesirable tendency. On the other hand, when it is lower than 1400 degreeC, a relative density will fall and it is unpreferable.

In addition, in this invention, the desired compounding ratio, mixing method, and shaping | molding method of a raw material powder are not specifically limited, Conventionally well-known various wet methods or dry methods can be used.

As a dry method, the cold press method, the hot press method, etc. are mentioned. In the cold press method, a mixed powder is filled into a molding die to produce a molded body, and then fired and sintered in an air atmosphere or an oxygen atmosphere. In the hot press method, the mixed powder is directly sintered in a mold.

As the wet method, for example, it is preferable to use a filtration molding method (see Japanese Patent Laid-Open No. 11-286002). This filtration molding method is a filtration molding die which consists of a non-aqueous material for depressurizing and draining water from a ceramic raw material slurry to obtain a molded body, and has a lower mold for molding having one or more drain holes and a cylinder placed on the lower mold for molding. It is composed of an aqueous filter and a molding die sandwiched from an upper surface side with a sealing material for sealing the filter therebetween, and assembled so that the lower mold, the molding die, the sealing member, and the filter can be disassembled, respectively. Using a filtration molding die for depressurizing and draining water in the slurry from only the filter face side, preparing a slurry composed of mixed powder, ion-exchanged water and an organic additive, and pouring the slurry into the filtration molding die, Ceramic molding obtained by producing a molded body by depressurizing and draining water in the slurry from only the filter surface side. A, it is fired and dried skim.

In each method, after sintering, machining for shaping | molding and processing to predetermined dimension is given, for example, as a target.

(Example)

Hereinafter, the present invention will be described based on specific examples.

(Example 1)

An indium oxide powder having an average particle diameter of 0.48 mu m, a tin oxide powder having an average particle diameter of 0.91 mu m, and a silicon oxide powder having an average particle diameter of 0.2 mu m were combined in a ratio of 85: 10: 5 by weight ratio. This was put into the resin pot and mixed for 21 hours by the dry ball mill. In this dry ball milling, a zirconium oxide ball was used as the media. The media and the raw material powder were classified by sifting, and a predetermined amount of 4% concentration of PVA binder was added to the obtained mixed powder and mixed. This powder was filled into a mold of size 236 × 440, and molded at a pressure of 800 kg / cm ² by the cold press method. This molded product was sintered in the air atmosphere as follows. It heated up at 60 degree-C / hour from room temperature to 1400 degreeC, hold | maintained at 1400 degreeC for 5 hours, and it lowered to 200 degreeC / hour to 1200 degreeC, and obtained the sintered compact. This sintered compact was processed to 6 inches (15.24 cm) in diameter, 5 mm in thickness, and metal-bonded to the backing plate made of oxygen-free copper, and the sputtering target was obtained. At the time of a process, the sputtering surface was grind | polished by the # 170 grinding wheel.

(Example 2)

A sintered compact was produced by the method similar to Example 1 except having changed the baking conditions of the molded object to the following method, and the sputtering target was obtained.

It heated up at 50 degree-C / hour from room temperature to 800 degreeC, hold | maintained at 800 degreeC for 4 hours, then heated up at 400 degree-C / hour to 1300 degreeC, heated up at 50 degree-C / hour to 1450 degreeC, and maintained at 1450 degreeC for 8 hours. After that, the temperature was lowered to 50 ° C./hour up to 800 ° C. Firing was carried out in an air atmosphere.

(Example 3)

A sintered compact was produced in the same manner as in Example 1 except that the average particle diameter of the silicon oxide powder was 0.6 µm, and the firing conditions of the molded body were changed to the following methods to obtain a sputtering target.

It heated up at 50 degree-C / hour from room temperature to 800 degreeC, hold | maintained at 800 degreeC for 4 hours, then heated up at 400 degree-C / hour to 1300 degreeC, heated up at 50 degree-C / hour to 1450 degreeC, and maintained at 1450 degreeC for 8 hours. After that, the temperature was lowered to 50 ° C./hour up to 800 ° C. Firing was carried out in an air atmosphere.

(Comparative Example 1)

A sintered compact was produced in the same manner as in Example 1 except that the average particle diameter of the silicon oxide powder was 0.05 µm to obtain a sputtering target.

(Comparative Example 2)

A sintered compact was produced in the same manner as in Example 1 except that the average particle diameter of the silicon oxide powder was 0.9 µm to obtain a sputtering target.

(Comparative Example 3)

A sintered compact was produced in the same manner as in Example 1 except that the average particle diameter of the silicon oxide powder was 1.5 µm to obtain a sputtering target.

(Comparative Example 4)

A sintered compact was produced in the same manner as in Example 1 except that the average particle diameter of the silicon oxide powder was 1.5 µm, and the firing conditions of the molded body were changed to the following methods to obtain a sputtering target.

It heated up at 50 degree-C / hour from room temperature to 800 degreeC, hold | maintained at 800 degreeC for 4 hours, then heated up at 400 degree-C / hour to 1300 degreeC, heated up at 50 degree-C / hour to 1450 degreeC, and maintained at 1450 degreeC for 8 hours. After that, the temperature was lowered to 50 ° C./hour up to 800 ° C. Firing was carried out in an air atmosphere.

(Comparative Example 5)

A sintered compact was produced by the method similar to Example 1 except having changed the baking conditions of the molded object to the following method, and the sputtering target was obtained.

It heated up at 60 degree-C / hour to 1100 degreeC, hold | maintained at 1100 degreeC for 5 hours, and it lowered to 200 degree-C / hour to 1000 degreeC, and obtained the sintered compact. Firing was carried out in an air atmosphere.

(Comparative Example 6)

A sintered compact was produced by the method similar to Example 1 except having changed the baking conditions of the molded object to the following method, and the sputtering target was obtained.

It heated up at 60 degree-C / hour to 1100 degreeC, hold | maintained at 1100 degreeC for 5 hours, and it lowered to 200 degree-C / hour to 1000 degreeC, and obtained the sintered compact. Firing was carried out in an oxygen atmosphere.

Relative Density Evaluation

The relative density was computed from the weight measured by the electronic balance about the sintered compact of Example 1-the comparative example 6, and the volume measured by the Archimedes method. At this time, the density of each raw material In ₂ O ₃ 7.179g / cm ³ , SnO ₂ density of 6.950g / cm ³ , SiO ₂ density of 2.200g / cm ³ and the weighted average calculated from the weighted average 100% I did it. For example, in the case of a raw material ratio of 85 wt% In ₂ O ₃ , 10 wt% SnO _2, and 5 wt% SiO ₂ , 6.430 g / cm ³ is 100% relative density. Table 1 shows the results of the relative density.

(Mechanical strength evaluation)

About the sintered compact of Example 1-the comparative example 6, the tensile strength was evaluated based on JISR1601 using the tensile strength tester. Table 1 shows the results of the tensile strength.

(Pinhole evaluation)

The sintered compacts of Examples 1 to 6 were pulverized, and the fracture surface was polished using a # 2000 sand paper until it became a mirror surface state by a rotary polishing machine, and binarized SEM image with a magnification of 100 times, Image processing software was used to count the number of pinholes having a diameter of 2 µm or more in the field of view. Table 1 shows the pinhole evaluation results.

(Evaluation of Area Ratio on Precipitation)

The sintered compacts of Examples 1 to 6 were pulverized, and the fracture surface was ground using a # 2000 sand paper until the mirror surface was polished by a rotary polishing machine, and the acid (HCl: H ₂ O) was maintained at 40 ° C. : HNO ₃ = 1: 1: 0.08 weight ratio), and the surface of the sintered compact was etched, and SEM image was taken at 5000 times magnification. As an example of evaluation results, SEM images of Examples 1 and 2 and Comparative Examples 2 and 5 are shown in FIGS. 1 to 4. The precipitated phase appeared as an etching residue as shown in FIGS.

This SEM image was binarized by image processing, and the area ratio with respect to the whole precipitated image was computed by image processing software. Table 1 shows the results of the area ratios. In addition, with respect to the connective these small, in addition, it was analyzed by the X-ray diffractometer, in Comparative Examples 5 and 6, a peak appeared on the In ₂ O ₃ phase and the In ₂ Si ₂ O _7. For Comparative Examples 5 and 6, the peaks of the In ₂ Si ₂ O ₇ phase did not appear. From the results of these SEMs and XRDs, the precipitated phase is considered to be an In ₂ Si ₂ O ₇ phase.

(Abnormal discharge evaluation)

Abnormal discharges were counted for the targets of Examples 1 to 6 using a DC magnetron sputtering apparatus and an arc (abnormal discharge) counter of the depot-down method. Table 1 shows the cumulative number of abnormal discharges generated during 73 hours of continuous sputter discharge under the following sputter conditions. However, for the target of Comparative Example 5, since the frequency of abnormal discharge rapidly increased after 38 hours from the discharge, the target was cracked by halting the discharge and observing the target by releasing the atmosphere. There was a trail. With respect to targets other than Comparative Example 5, when the target residual thickness after discharge for 73 hours was measured using a three-dimensional measuring instrument, all were 0.5 mmt or less, and it was confirmed that they were used until the end of the target life. In addition, when the target was observed with the naked eye, no targets were cracked, cracked or cracked.

(Sputter condition)

Reach Pressure 1 × 10 ^-4 Pa

Heating temperature 100 ℃

Argon partial pressure 0.5Pa

Oxygen partial pressure 5 × 10 ^-3 Pa

DC power 300W

73 hours discharge time

Glass substrate Corning Corporation # 1737 (both side polished products)

(Time-dependent change of film characteristics)

During the continuous discharge described above, after 10 hours, 40 hours, and 70 hours had elapsed from the start of discharge, a 200 nm ITO film was formed on the glass substrate. The sheet resistance was measured by the four probe method, and the change over time was evaluated. The results are shown in Table 1.

(Smooth Surface of Film)

In Examples 1-3 and Comparative Examples 1, 2, 4, and 5, the surface roughness of 10 micrometers square was evaluated by the surface shape measuring instrument AFM about the 200-nm film formed after 40 hours of said passage. The results are shown in Table 1.

(Evaluation device)

Electronic scale GP3400IP made in Sartorius

SEM JSM-6380A JEOL Corporation

Image Processing Software Particle Analysis III

X-ray diffractometer MXP3 manufactured by MAC Science

X-ray Diffraction Measurement Conditions

Sailor CuKα ₁ λ = 1.5405

Tube voltage 40kV

Tube current 30mA

20 to 40 ° measuring range

Sampling interval 0.02 °

Scan Speed 4 ° / min.

Divergence Slit 1 °

Scattering Slit 1 °

Light Receiving Slit 0.3mm

Section tester Autograph made by Shimadzu Corporation

Arc Counter Arc Monitor Landmark

3D Measuring Machine GJ1000D Tokyo Precision

Sheet resistance measuring instrument MCP-TP06P diamond instrument company made

Surface shape measuring instrument AFM SPI3700 (manufactured by SII Corporation)

(Test result)

As is clear from the results shown in Table 1, Examples 1 to 3 in which the average particle diameter of the silicon oxide raw material powder was 0.2 to 0.6 µm and the firing temperature was 1400 ° C. or higher improved the density of the sintered body and the pinholes inside the sintered body. It was found that this decreased and the precipitated phase increased.

In this way, the sintered body density was improved, so that the mechanical strength was increased, and cracks and cracks of the sintered body at the time of abnormal discharge occurrence and thermal shock were suppressed, and sputtering also confirmed that a smooth film having small Ra and Ry was obtained. Moreover, it was also confirmed that abnormal discharge at the time of sputtering was suppressed by pinhole reduction, and the smooth film | membrane with small Ra and Ry is obtained by sputter | spatter. Further, it was confirmed that the increase in the precipitation phase resulted in a change in the characteristics of the sputtered film from the beginning to the end of the target use over time, and a smooth film having a small Ra and Ry was obtained by the sputtering.

On the other hand, in the case of Comparative Example 1 in which the average particle diameter of the silicon oxide raw material powder was 0.05 µm, or Comparative Examples 2 and 4 in which the average particle diameter was 0.9 µm or 1.5 µm, the relative density was less than 102% and the number of pinholes was also large. Also, the precipitated phase was less than 40%, and Ry became a large film. In addition, even when the average particle diameter of the silicon oxide raw material powder is 0.2 µm, when the firing temperature is low at 1100 ° C, the relative density is remarkably small and the pinhole number is remarkably increased, and the abnormal discharge is remarkably increased. It was found that Ra and Ry became a big film.

The present invention, for example, when used as a sputtering target, the oxide sintered body which can achieve a stable sputter discharge from the beginning to the end of use, and can realize a transparent conductive film with a small Ra or Ry used for organic EL, high-definition LCD, etc. The effect of providing the manufacturing method, a sputtering target, and a transparent conductive film can be acquired.

Claims (9)

An oxide sintered body containing indium oxide and tin oxide as necessary and containing silicon oxide, wherein the oxide sintered body has a relative density of 102% or more. The oxide sintered body according to claim 1, wherein the number of pinholes having a Feret diameter of 2 µm or more in the sintered body is 50 pieces / mm ² or less per unit area. The oxide sintered compact according to claim 1, wherein the ratio of the precipitated phase when the microscopic observation of any cross section of the sintered compact is 40% or more in area ratio. The oxide sintered compact according to claim 2, wherein the ratio of the precipitated phase when the microscopic observation of any cross section of the sintered compact is 40% or more in area ratio. In the method for producing an oxide sintered body containing indium oxide and tin oxide as necessary and containing silicon oxide, the average particle diameter of the silicon oxide raw material powder is 0.2 μm to 0.6 μm, and then mixed with other raw material powder, and then fired. Sintering is carried out at the temperature of 1400 degreeC or more, and the oxide sintered compact whose relative density is 102% or more is obtained, The manufacturing method of the oxide sintered compact. delete The sputtering target which bonded the oxide sintered compact of any one of Claims 1-4 to the backing plate. 8. The sputtering target according to claim 7, wherein the maximum smoothness (Ry) of the surface smoothness of the transparent conductive film formed by sputtering at a thickness of 200 nm on the glass substrate is 6.0 nm or less. A transparent conductive film formed by sputtering by using the sputtering target according to claim 7, wherein the surface smoothness of the transparent conductive film formed on the glass substrate with a film thickness of 200 nm by sputtering has a maximum height difference (Ry) of 6.0 nm or less. Transparent conductive film.

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