KR100581138B1 - Tin oxide powder for ito sputtering target, sintered body sputtering target for ito film fomation and production method of target - Google Patents

Abstract

The slurry of tin oxide powder having a solid content of 65% or more is pulverized in a wet zirconia beads mill, and the median diameter obtained from the particle size distribution is in the range of 0.40 to 1.0 μm, and the 90% particle size determined in the particle size distribution is in the range of 3.0 μm or less. The present invention provides a method for producing tin oxide powder for an ITO sputtering target, wherein the zirconium content is less than 100 ppm and the remainder is made of tin oxide. Provided is a method for producing a tin oxide-indium oxide target for forming an ITO film which can suppress the deterioration of the quality of a thin film.

ITO sputtering target, tin oxide powder, sintered body for ITO film formation

Description

TIN OXIDE POWDER FOR ITO SPUTTERING TARGET, SINTERED BODY SPUTTERING TARGET FOR ITO FILM FOMATION AND PRODUCTION METHOD OF TARGET}

The present invention relates to a sintered compact sputtering target most suitable for forming tin oxide powder for an ITO sputtering target and an ITO film for forming an ITO film and a method of manufacturing the same.

ITO (indium-tin composite oxide) film is widely used as a transparent electrode (film) of a display device centered on a liquid crystal display.

As a method of forming this ITO film, it is common to carry out by means generally called a physical vapor deposition method, such as a vacuum vapor deposition method and sputtering method. In particular, it is often formed using the magnetron sputtering method because of the operability and the stability of the film.

The formation of the film by the sputtering method physically collides positive ions such as Ar ions with a target provided on the cathode, releases the material constituting the target by the collision energy, and faces the anode. This is carried out by laminating a film having a composition substantially the same as that of the target material on the substrate on the) side.

The coating method by the sputtering method is characterized by forming a thin film of several tens of micrometers from a thin film in the unit of an angstrom at a stable film forming speed by controlling the processing time, the power supply, and the like.

Particularly problematic in the case of forming the ITO film is the formation of a protrusion called a row in the aerozone portion of the ITO target or its surroundings. When this line is generated, the sputter rate is lowered or abnormal discharge (micro arcing) is caused to significantly reduce productivity.

In addition, coarse particles (particles) appear to float in the sputter chamber due to nodules and abnormal discharges, and they reattach to the formed thin film, causing defects (pin holes) or projections of the thin film. This results in a problem that the quality of the film decreases.

As a countermeasure for suppressing the generation of nodules, it is generally known to increase the density of a target and to reduce pores in the target.

In addition, it is effective to reduce the disparity in the composition in the target by miniaturizing indium oxide and tin oxide which are the raw material powders of the target sintered compact and improving their respective dispersibility. In particular, when the grains of tin oxide coarsen, it cannot be sufficiently dissolved in the mixed indium oxide, and it exists as a lump of tin oxide in the sintered compact, and thus becomes a starting point of the furnace line during sputtering. Moreover, they become a cause of the voids in a sintered compact, and become a factor which inhibits the densification of a sintered compact.

In order to refine the tin oxide powder, the method of mechanically grinding the raw material powder is the simplest and the lowest cost. Generally known as a grinding apparatus, there are a jet mill which grind | pulverizes by mutual collision of a raw material or a liner, and the bead mill which grind | pulverizes by grinding between media or a liner using grinding media. However, in the jet mill method, in order to grind a hardly cohesive raw material such as tin oxide powder to the particle size of the sub-micron region, an extreme decrease in throughput, such as an increase in the number of passes, is incurred. It is called as.

From this, the powder for sintering of the ITO target is preferably a media stirring grinder, and a wet bead mill that is easy to control the aggregation of raw materials is most suitable.

In this beads mill grinder, increasing the grinding power or the number of passes is more finely differentiated, but if it is too strong, the grinding amount becomes difficult to control, and if it is too weak, the movement of beads and slurry in the mill becomes poor and the grinding efficiency is remarkable. In order to reduce, it is required to perform pulverization by controlling to an appropriate strength.

The indium oxide powder, which is a raw material powder of the ITO target, is easily pulverized and has no particular problem, but a hard and cohesive powder such as tin oxide is more difficult to pulverize than the indium oxide powder. Therefore, as a raw material powder, especially grinding of tin oxide is a problem, and it is necessary to control this.

In crushing tin oxide, it is generally thought that finer grinding can be achieved by increasing the grinding power or the number of passes, but in addition to the problem of increasing the grinding power or the number of passes, a liner or There is a problem that hard bead materials and the like are mixed as contaminants in the tin oxide powder.

Therefore, the problem of the densification by sintering using the granulated powder and the contamination of the sintered material due to the delamination are inconsistent with each other, and an optimum powder for densification is obtained. What cannot be said is the present situation.

As mentioned above, although ITO thin film formation needs to obtain a uniform and high density sintered compact target, there exists a problem that the optimal tin oxide powder and high density sintered compact target which can satisfy these requirements are not obtained.

(Initiation of invention)

The present invention provides a tin oxide powder capable of solving the above-mentioned problems, in particular, a sintered compact having the highest density and uniformity of components most suitable for forming an ITO thin film, a sputtering target for forming an ITO film sintered using the powder, and The present invention provides a method for producing the tin oxide-indium oxide target for forming an ITO film, which can suppress deterioration in the quality of the thin film and the resulting thin film formed during the formation of the ITO thin film. It is for the purpose.

It has been found that the technical means for solving the above problems is to strictly control the particle size of the tin oxide powder, whereby a sputtering target most suitable for an ITO transparent conductive film or the like can be obtained.

Based on this finding, this invention,

l. A slurry of tin oxide powder having a solid content of 65% or more is pulverized in a wet zirconia bead mill, and the median diameter obtained from the particle size distribution ranges from 0.40 to 1.0 μm, and the 90% particle size determined from the particle size distribution is 3.0 μm or less. A method for producing tin oxide powder for an ITO sputtering target, wherein the zirconium content is less than 100 ppm and the balance consists of tin oxide.

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2. The slurry of tin oxide powder having a solid content of 65% or more is pulverized in a wet zirconia bead mill, and the median diameter obtained from the particle size distribution is in the range of 0.40 to 1.0 μm, and the 90% particle size determined from the particle size distribution is in the range of 1.0 μm or less. A method for producing tin oxide powder for an ITO sputtering target, wherein the zirconium content is less than 100 ppm and the balance consists of tin oxide.

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3. The median diameter obtained from the particle size distribution ranges from 0.40 to 1.0 µm, and the 90% particle size obtained from the particle size distribution falls within the range of 3.0 µm or less, and the slurry of tin oxide powder having a solid content of 65% or more is pulverized in a wet zirconia beads mill. A method of producing a sputtering target for forming an ITO film, characterized by sintering using a tin oxide powder and an indium oxide powder.

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4. The median diameter obtained from the particle size distribution ranges from 0.40 to 0.60 µm, and the 90% particle size obtained from the particle size distribution falls within the range of 1.0 µm or less. A method of producing a sputtering target for forming an ITO film, characterized by sintering using a tin oxide powder and an indium oxide powder.

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5. Production of ITO film-shaped sputtering target according to 3) or 4) above, wherein the zirconium content is less than 100 ppm and the remainder is sintered tin oxide and indium oxide powder composed of tin oxide. Way.
To provide.

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To provide.

(Embodiment of invention)

In the present invention, the tin oxide powder for the ITO sputtering target has a median diameter of 0.10 to 1.0 µm in the particle size distribution, and the 90% particle size obtained in the particle size distribution is in the range of 3.0 µm or less, and preferably, the particle size. The median diameter obtained from the distribution is in the range of 0.40 to 0.60 m, and the 90% particle size obtained from the particle size distribution is in the range of 1.0 m or less.

The conventional tin oxide powder has a value of 50% of the integrated volume frequency obtained from the particle size distribution = 1.5-2.5 μm of median diameter, and a 90% of the integrated volume frequency obtained from the particle size distribution = 90% particle size. It was the range of about 5.0-10.0 micrometers.

The tin oxide powder is mixed with the indium oxide powder in a predetermined ratio and ground to a median diameter of about 0.5 to 1.0 mu m with a wet bead mill. However, the tin oxide powder in the mixed powder was not sufficiently dispersed, and some existed as coarse grains of about 5 to 10 µm. Such coarse grains of tin oxide cannot be sufficiently dissolved in indium oxide and cause tin oxide lumps or pores in the sintered compact, so that the sintered compact does not sufficiently increase and a uniform and high-density sintered compact cannot be obtained.

Since the components of the sintered compact are not uniform and sufficient density is not obtained in this way, there is a problem that a gap occurs during sputtering film formation, resulting in a decrease in the quality of the ITO film.

As a result of finding the cause, the median diameter obtained from the particle size distribution of the tin oxide powder ranges from 0.40 to 10 µm, focusing on the fact that the particle size of the tin oxide powder is important and that the coarse grains contained in the raw material reduce the density of the sintered compact. In addition, the 90% particle size obtained from the particle size distribution is in the range of 3.0 μm or less, preferably the median diameter obtained from the particle size distribution is in the range of 0.40 to 0.60 μm, and the 90% particle size obtained from the particle size distribution is l.0. By setting it as the range of micrometer or less, it succeeded in obtaining a high density and high quality sintered compact.

By using the said powder of this invention, the sintered compact provided with the highest density of 7.12 g / cm <^3> or more or 7.13 g / cm <^3> or more which is the best density for an ITO sputtering target can be obtained.

At the time of pulverization, the particle size of tin oxide is adjusted by selection of raw material powder, adjustment of grinding power, recovery of passes, adjustment of diameter and material of grinding beads, and adjustment of solid content of tin oxide powder slurry. This can be done by appropriately controlling the conditions to be achieved.

Although zirconia beads are used as the grinding media, due to the problem of contaminants of zirconium, it is possible to suppress the problem of contaminants by using a tin oxide powder slurry having a solid content of 65% or more.

Thereby, the sintering powder which can be grind | pulverized without difficulty and has the outstanding sinterability can be obtained.

1 is a diagram showing sputter integration power and nodule coverage at the time of sputtering the sputtering targets produced in Examples 1 and 2 and Comparative Example, and FIG. 2 is a sputtering target produced in Examples 1, 2 and Comparative Example. Fig. 3 shows the sputter integration power and the number of micro arcing at the time of sputtering of the trace, and Fig. 3 is a diagram showing the median and Zr contaminant amounts at each solid content concentration of the tin oxide powder slurry prepared in Example 3.

Next, examples of the present invention will be described. In addition, an Example is an example to the last and is not limited to this example. That is, all the aspects or modifications except an Example are included within the scope of the technical idea of this invention.

Example 1

A mediator having a solid content of 65% was prepared by mixing a tin oxide powder having a median diameter of 2.0 μm, a 90% particle size of 3.50 μm, and a BET specific surface area of 4.0 m ² / g with pure water. For particle size distribution measurement, a laser diffraction / scattering particle size distribution meter (LA-920 manufactured by Horiba, Ltd.) and a continuous flow surface area meter (SA-6200 manufactured by Horiba, Ltd.) were used for the BET specific surface area. At this time, in order to disperse the tin oxide powder in pure water, ammonia water was added to adjust the pH of the slurry to 9.0.

Next, the produced slurry was pulverized as a bead mill, and the median diameter obtained from the particle size distribution was pulverized to 1.0 m, 90% of the particle diameter was 2.0 m, and the BET specific surface area was 6.0 m ² / g. At this time, zirconia beads (YTZ) were used for the grinding beads in consideration of wear resistance.

Tin oxide 1: indium oxide hexavalent as a solid content weight ratio of indium oxide powder having a median diameter of 2.0 m, a 90% particle diameter of 3.0 m, and a BET specific surface area of 8.0 m ² / g obtained from the pulverized tin oxide slurry and particle size distribution as described above. It was mixed with pure water as much as possible, and the slurry of 50% of solid content was produced.

Next, the produced tin oxide and indium oxide mixed slurry were ground and mixed as a bead mill, and the median diameter obtained from the particle size distribution was 0.80 µm, the 90% particle diameter was 1.50 µm, and the BET specific surface area was ground to 10 m ² / g.

Next, a binder was added to this pulverized slurry and granulated and dried as a spray dryer. After filling the dried powder into a mold, it was molded at a pressure of 100 kgf / cm ^{2 with} a hydraulic press, and then again at a pressure of 1500 kgf / cm ^{2 with} a cold isostatic hydrostatic press (CIP) to obtain a density of 4.0 g / cc. A molded article was obtained.

Next, the sintered compact obtained as a result of sintering this molded body at the sintering temperature of 1550 degreeC for 4 hours in oxygen atmosphere was obtained by the high density sintered compact of 7.128 g / cm < ³ > by the Archimedes method.

However, when this molded object was sintered at a sintering temperature of 1500 ° C, only a density of 7.97 g / cm ³ could be achieved.

Example 2

As the same grinding conditions as in Example 1, the median diameter obtained from the particle size distribution was 0.5 µm, the 90% particle diameter was 0.80 µm, and the BET specific surface area was ground to 7.0 m ² / g.

Next, pulverized tin oxide slurry and an indium oxide powder having a median diameter of 2.0 µm, a 90% particle diameter of 3.0 µm, and a BET specific surface area of 8.O m ² / g obtained from the particle size distribution were mixed with pure water, and then mixed with pure water. In the same manner, the median diameter was ground to 0.80 µm, the 90% particle diameter to 1.50 µm, and the BET specific surface area to 10 m ² / g.

This ground slurry was granulated and dried in the same manner as in Example 1. Next, the obtained powder was filled into a mold, and then molded at a pressure of 100 kgf / cm ^{2 with} a hydraulic press, and then again molded at a pressure of 1500 kgf / cm ^{2 with} a cold isostatic hydrostatic press (CIP) to obtain a density of 4.0 g /. A molded article of cc was obtained.

Next, the sintered compact obtained as a result of sintering this molded object at the sintering temperature of 1550 degreeC for 4 hours and oxygen atmosphere was obtained by the high density sintered compact of 7.129 g / cm < ³ > by the Archimedes method.

Moreover, when this molded object was sintered at sintering temperature 1500 degreeC, the high density sintered compact of density 7.130g / cm <^3> was obtained.

(Comparative Example 1)

Median diameter 2.0 µm from the particle size distribution, 3.50 µm in 90% particle size, 4.0 m ² / g tin oxide powder with BET specific surface area and median diameter 2.0 µm, 3.0 µm in 90% particle size and BET specific surface area from particle size distribution 8.O m ² / g of indium oxide powder was mixed with pure water so as to have tin oxide 1: indium oxide 9 as a solid content weight ratio in the same manner as in Example to prepare a slurry having a solid content of 50%.

Next, by the same method as in Example 1, the median diameter obtained from the particle size distribution was 0.80 µm, the 90% particle diameter was 1.50 µm, and the BET specific surface area was ground to 10 m ² / g.

A binder was added to this ground slurry and granulated and dried in the same manner as in Example 1. After the obtained powder was filled into a mold, it was molded at a pressure of 100 kgf / cm ^{2 with} a hydraulic press, and then again molded at a pressure of 1500 kgf / cm ^{2 with} a cold isostatic hydrostatic press (CIP) to form a compact having a density of 4.0 g / cc. Got.

Next, the density of the sintered compact obtained as a result of sintering this molded body at the sintering temperature of 1550 degreeC for 4 hours and oxygen atmosphere reached only 7.101 g / cm <^3> by the Archimedes method. Moreover, even when the sintering temperature was raised to 1650 degreeC, the density of the sintered compact was 7.108 g / cm <^3> .

The sintered bodies produced in Examples 1 and 2 and Comparative Example 1 were subjected to mechanical processing to produce sputtering targets, and measure the amount of nodules (covering rate) during sputtering and the number of abnormal discharges (microarking) during sputtering targets. It was.

The conditions of sputtering are as follows.

  Target size: 127 × 508 × 6.35 mm

Sputter Gas: Ar + O ₂

  Sputter Gas Pressure: 0.5 Pa

  Sputter Gas Flow Rate: 300 SCCM

  Oxygen Concentration in Sputter Gas: 1 Vol%

  Leakage magnetic flux density: 0.l T

Input sputter power density: Sputtering starts at 0.5 W / cm ² to keep the film formation rate constant

                          To increase.

Integrated power of sputter: ~ 160 WHr / cm ²

The amount of nodules generated in FIG. 1 and the number of micro arcing in FIG. 2 are shown. The amount of nodules generated (coating rate) was calculated as a value obtained by dividing the image of the target portion of the target by a computer, and dividing the area of the generated nodules by the area of the erosion. The microarking threshold value was set to detection voltage: 100 V or more and discharge energy (sputtering voltage at the time of arc discharge x sputtering current x generation time): 10 mJ or less.                 

As apparent from Fig. 1, the target of the comparative example rapidly increases the nodules from the accumulated power of 40 WHr / cm ² , and at the end-of-life integrated power of 160 WHr / cm ² , 40% or more of the nodules are applied. Even if the targets of Examples 1 and 2 were sputtered up to an integrated power of 160 WHr / cm ² , the amount of nodules generated was 0%, indicating that they were remarkably excellent.

In addition, also in the number of micro arcing of FIG. 2, the target of the comparative example rapidly increased the arcing number at the integrated power of 80 WHr / cm ² , whereas the targets of Examples 1 and 2 had a small number of arcing times and stable film forming conditions. It was found that obtained.

Comparing Examples 1 and 2, no difference was found in the amount of nodules, but when the number of arcing was compared, it was found that Example 2 was better.

Example 3

The amount of impurities in the zirconia beads when preparing the tin oxide powder used in Examples 1 and 2 was investigated. For the grinding, the beads mill used in the above example was used, and the grinding beads were Zr beads (YTZ) having a diameter of 0.5 mm.

The tin oxide powder was mixed with pure water so as to be 25%, 45%, and 65% by weight of solids, respectively. At this time, in order to disperse tin oxide powder in pure water, ammonia water was added, pH was adjusted to 8.0-10.0, and the viscosity of the slurry was adjusted to 0.1 Pa * s or less. The slurry of each said solid content was run under the same grinding | pulverization conditions, and the amount of Zr mixed with each grinding particle diameter was investigated. As a result, as compared with the same particle diameter as shown in Fig. 3, it was found that the higher the solid content, the smaller the amount of Zr contained.

It has a remarkable feature that it is possible to obtain a sintered compact having the highest density and uniformity of components that are most suitable for forming ITO thin films. It has the outstanding effect that the tin oxide-indium oxide target for ITO film formation which can be suppressed can be obtained at low cost.

Claims (10)

delete delete The slurry of tin oxide powder having a solid content of 65% or more is pulverized as a wet zirconia bead mill, and the median diameter obtained from the particle size distribution is in the range of 0.40 to 1.0 μm, and the 90% particle size obtained from the particle size distribution is 3.0 μm. The manufacturing method of the tin oxide powder for ITO sputtering targets of the following ranges, The zirconium content is less than 100 ppm, and remainder consists of tin oxide. A slurry of tin oxide powder having a solid content of 65% or more is pulverized as a wet zirconia bead mill, and the median diameter obtained from the particle size distribution is in the range of 0.40 to 1.0 μm, and the 90% particle size obtained from the particle size distribution is 1.0 μm. The manufacturing method of the tin oxide powder for ITO sputtering targets of the following ranges, The zirconium content is less than 100 ppm, and remainder consists of tin oxide. delete delete delete The tin oxide powder obtained by pulverizing a slurry of tin oxide powder having a solid content of 65% or more with a median diameter of 0.40 to 1.0 μm in the particle size distribution and a range of 3.0 μm or less in a particle size distribution as a wet zirconia beads mill. A method for producing a sputtering target for forming an ITO film, which is sintered using an indium oxide powder. The tin oxide powder obtained by pulverizing a slurry of tin oxide powder having a solid content of 65% or more with a median diameter of 0.40 to 0.60 µm in a particle size distribution and a range of 1.0 µm or less in a particle size distribution as a wet zirconia beads mill. A method for producing a sputtering target for forming an ITO film, which is sintered using an indium oxide powder. 10. The method for producing a sputtering target for forming an ITO film according to claim 8 or 9, wherein a zirconium content is less than 100 ppm and the remainder is sintered tin oxide and indium oxide powder composed of tin oxide. .

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