WO2017158928A1 - 酸化物焼結体 - Google Patents
酸化物焼結体 Download PDFInfo
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- WO2017158928A1 WO2017158928A1 PCT/JP2016/084248 JP2016084248W WO2017158928A1 WO 2017158928 A1 WO2017158928 A1 WO 2017158928A1 JP 2016084248 W JP2016084248 W JP 2016084248W WO 2017158928 A1 WO2017158928 A1 WO 2017158928A1
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Definitions
- the present invention relates to an oxide sintered body for a sputtering target suitable for forming a transparent conductive film in a flat panel display or the like.
- An ITO (Indium Tin Oxide) film has features such as low resistivity, high transmittance, and ease of microfabrication, and these features are superior to other transparent conductive films. It is used in a wide range of fields including electrodes. At present, most of the ITO film forming methods in industrial production processes are so-called sputter film forming methods in which sputtering is performed using an ITO sintered body as a target because it can be produced in a large area with good uniformity and productivity.
- Patent Documents 1 to 3 disclose that Mg-containing ITO thin films have a flat film surface, improved etching characteristics, and improved film durability (moisture resistance and high temperature resistance).
- Patent Documents 4 to 6 describe that a stable amorphous film is formed without adding water at the time of film formation, and etching residues are reduced.
- Patent Document 7 discloses a sintered body in which ITO contains 5 to 5000 ppm of one or more elements selected from five kinds of elements such as Mg and has an improved density.
- Patent Documents 8 to 9 disclose high-strength ITO sputtering targets containing 0.001 to 0.1 wt% of an oxide of at least one element of Mg, Ca, Zr, and Hf. Yes. This is because strength is improved by adding a small amount of oxide such as Mg, but on the other hand, since the addition amount is too small, the above-mentioned effects such as amorphous stabilization of the film can be obtained. Absent.
- the bending strength is measured in accordance with JIS R1601, and according to the JIS standard, the surface roughness Ra of the test piece is 0.2 ⁇ m or less.
- the strength of ceramics is greatly affected by the surface roughness, for example, even if Ra is 0.2 ⁇ m or less, when Ra is slightly below 0.2 ⁇ m, and when the surface roughness is smaller by an order of magnitude Therefore, it is necessary to consider the point that the strength is greatly different.
- a great cost is generated, which is not preferable for industrial production.
- a sintered body (target) having high mechanical strength within the practical surface roughness range as well as the effects of improving the durability of the film and stabilizing the amorphous state of the film. Yes.
- Japanese Patent No. 3632524 Patent No. 4075361 Japanese Patent No. 3215392 Patent No. 4885274 Patent No. 4,489,842 Japanese Patent No. 5237827 Japanese Patent No. 3827334 Japanese Patent No. 4855964 Patent No. 5277284
- the present invention is an oxide sintered body for a sputtering target for forming an Mg-containing ITO film having excellent amorphous stability and durability, and the generation of cracks in the target and generation of particles during sputtering are greatly reduced. It is an object of the present invention to provide an oxide sintered body having a high bending strength that can be suppressed.
- the present inventor has conducted extensive research, and as a result, by appropriately adjusting the composition and sintering conditions of the sintered body, the bending strength of the sintered body (sputtering target) is improved. As a result, it was found that the generation of nodules can be suppressed, the generation of arcing and particles during sputtering can be suppressed, and the yield of the film forming process can be improved. Based on the above findings, the present inventors provide the following invention.
- the oxide sintered body according to claim 1 or 2 wherein the number of pores having an equivalent circle diameter of 0.1 ⁇ m or more is 30 or less in an area of 80 ⁇ 120 ⁇ m 2 .
- the present invention can achieve high bending strength by appropriately adjusting the composition of the sintered body and the sintering conditions in the oxide sintered body substantially composed of indium, tin, magnesium and oxygen. Thus, there is an excellent effect that the generation of particles during sputtering is small and stable sputtering is possible.
- the oxide sintered body of the present invention is substantially composed of indium, tin, magnesium and oxygen, wherein tin is a Sn / (In + Sn + Mg) atomic ratio of 5 to 15%, and magnesium is Mg / (In + Sn + Mg). It is contained in an atomic ratio of 0.1 to 2.0%, with the balance being indium and oxygen.
- Sn represents the number of tin atoms
- In represents the number of atoms of indium
- Mg represents the number of atoms of magnesium, respectively.
- the total number of atoms of indium, tin, and magnesium, which are all metal atoms, of tin and magnesium The appropriate concentration range of the atomic ratio is shown respectively.
- the sputtering target can be produced by processing the oxide sintered body into a predetermined diameter and thickness, and the transparent conductive film can be obtained by sputtering the sputtering target.
- the composition of the sputtering target and the oxide sintered body is the same, and there is almost no difference in composition between the sputtering target and the film obtained by sputtering.
- “Substantially” means that the constituent element of the oxide sintered body is formed from only four types of indium, tin, magnesium, and oxygen, but is included in normally available raw materials, and the raw material production Even if inevitable impurities that cannot be removed by the usual purification method are included in the inevitable concentration range, the present invention shows that the concept includes them. That is, inevitable impurities are included in the present invention.
- tin When tin is added to indium oxide, it functions as an n-type donor and has the effect of reducing resistivity.
- magnesium When magnesium is added to ITO, it has the effect of preventing the crystallization of the film and making it amorphous.
- Mg Mg / (In + Sn + Mg) ⁇ 0.1%
- Mg / (In + Sn + Mg)> 2.0% the annealing temperature necessary to crystallize the amorphous film obtained by sputtering becomes higher than 260 ° C. The cost, labor, and time for implementing such a process are inadequate for production.
- the magnesium concentration is optimally 0.1 to 2.0% in terms of the atomic ratio of Mg / (In + Sn + Mg) as defined in the present invention. The magnesium concentration is thus determined.
- the oxide sintered body having the above composition has a bending strength of 140 MPa or more when the surface roughness Ra is 0.3 to 0.5 ⁇ m.
- the bending strength is measured by a three-point bending test in accordance with JIS R1601: 2008. Specifically, the sample total length: 40 mm ⁇ 0.1 mm, width: 4 mm ⁇ 0.1 mm, thickness: 3 mm ⁇ 0.1 mm, distance between fulcrums: 30 mm ⁇ 0.1 mm, crosshead speed: 0.5 mm / min And the average value for 10 samples.
- the sintered body When the bending strength is less than 140 MPa, when excessive power is applied at the time of sputtering, the sintered body is caused by stress generated by the difference in thermal expansion between the sputtering target (sintered body) and the backing plate bonding the target. May crack. Also, arcing and particles may increase during sputtering.
- the oxide sintered body of the present invention preferably has a density of 7.1 g / cm 3 or more. Increasing the density of the sintered body (target) has an excellent effect of improving the uniformity of the sputtered film and significantly reducing the generation of particles during sputtering.
- the sintered body density is obtained by the Archimedes method by dividing the measurement results at each of the five samples taken from the vicinity of the center and the four corners of the rectangular flat plate target by the number of measurement points.
- the number of pores having an equivalent circle diameter of 0.1 ⁇ m or more is preferably 30 or less in an area of 80 ⁇ 120 ⁇ m 2 . Due to insufficient sintering, a sufficient reaction is not performed between the raw materials, and many pores are generated in the sintered body. The presence of such pores decreases the bending strength of the sintered body, increases the variation in the bending strength, and also causes the generation of nodules. Therefore, it is preferable to reduce it as much as possible. Regarding the number of pores, a sample having a size of about 1.5 cm square is cut out from the sintered body (center portion), and the cut surface is polished to a mirror surface, and then the structure is observed with an electron microscope. Then, the number of pores with an equivalent circle diameter of 0.1 ⁇ m or more existing in an area of 80 ⁇ 120 ⁇ m 2 observed at a magnification of 1000 is counted.
- each raw material powder is mixed and pulverized at a predetermined ratio to form a slurry, and the slurry is dried with a spray dryer to form a granulated powder. Molding and sintering.
- “magnesium oxide” is used as a raw material, the viscosity of the slurry does not increase, and there is a problem that mixing, pulverization and granulation are difficult. Insufficient mixing of raw material powders may cause warpage and cracks in the sintering process, and the density of the sintered body will not be sufficiently increased.
- nodules are generated and abnormal discharge is caused.
- a high resistivity region and a low resistivity region in which magnesium oxide is segregated exist on the target, and abnormal discharge is more likely to occur.
- magnesium hydroxide and magnesium carbonate hydroxide are decomposed by heating to release water and carbon dioxide, they are extremely inappropriate as raw materials for producing a high-density sintered body. Further, when using magnesium indium acid or magnesium stannate, it is necessary to synthesize those raw materials in advance, which significantly reduces productivity.
- the tin oxide raw material and the magnesium oxide raw material are mixed and pulverized into a slurry, and separately mixed with the indium oxide raw material obtained as a pulverized slurry. Even when magnesium oxide is used as a raw material, a high-density sintered body can be obtained.
- the method for producing the oxide sintered body of the present invention will be specifically described below.
- the oxide sintered body of the present invention is not limited to the following production method, and the production conditions and the like can be appropriately changed within a range that does not greatly change the characteristics of the oxide sintered body.
- a predetermined amount of tin oxide and magnesium oxide is weighed, an appropriate amount of pure water is added, sufficient mixing is performed using a mixer, and the mixture is finely pulverized into a slurry by a bead mill.
- a predetermined amount of indium oxide is weighed, pure water is added and mixed and pulverized to obtain a slurry.
- the viscosity of the slurry can be adjusted by adjusting the pH using an acid or an alkali as necessary.
- the atmospheric gas may be the air because it is not necessary to take into consideration the oxidation of the raw material.
- a slurry in which tin oxide and magnesium oxide are mixed and a slurry of indium oxide are mixed with a mixer and pulverized by a bead mill to obtain a slurry in which raw material powders are uniformly mixed.
- the fine pulverization is desirably performed until the average particle diameter (D50) is 1 ⁇ m or less, preferably 0.6 ⁇ m or less.
- granulation is performed. This is to improve the fluidity of the raw material powder and to make the filling state during press molding sufficiently satisfactory.
- PVA polyvinyl alcohol
- granulator inlet temperature is 200 to 250 ° C.
- outlet temperature is 100 to 150 ° C.
- disk rotation speed is 8000 to 10,000 rpm.
- press molding is performed.
- a granulated powder is filled into a mold of a predetermined size and uniaxially pressed under conditions of a surface pressure of 40 to 100 MPa and held for 1 to 3 minutes to obtain a compact.
- a surface pressure 40 to 100 MPa
- the surface pressure does not need to exceed 100 MPa, and wasteful cost and energy are required, which is not preferable for production.
- CIP molding is performed.
- the molded body obtained above is vacuum-packed twice with vinyl and subjected to CIP (cold isotropic pressure method) under the conditions of pressure 150 to 400 MPa and holding for 1 to 3 minutes. If the pressure is less than 150 MPa, sufficient CIP effect cannot be obtained. On the other hand, even if a pressure of 400 MPa or more is applied, the density of the molded body is not easily improved beyond a certain value. Surface pressure is not particularly required for production.
- the sintering temperature is 1500 to 1600 ° C.
- the holding time is 4 to 20 hours
- the heating rate is 1 to 5 ° C./min
- the temperature is lowered by furnace cooling.
- the sintering temperature is lower than 1500 ° C.
- the density of the sintered body is not sufficiently increased, and when it exceeds 1600 ° C., the life of the furnace heater is reduced.
- the holding time is shorter than 4 hours, the reaction between the raw material powders does not proceed sufficiently and the density of the sintered body does not increase sufficiently. Even if the sintering time exceeds 20 hours, the reaction has sufficiently occurred, and unnecessary energy and time are wasted, which is not preferable for production.
- the rate of temperature rise is slower than 1 ° C / min, it will take unnecessary time to reach the predetermined temperature, and if the rate of temperature rise is faster than 5 ° C / min, the temperature distribution in the furnace will be uniform. It will not rise and cause unevenness.
- D50 average particle diameter
- a slurry in which tin oxide and magnesium oxide were mixed and a slurry of indium oxide were mixed with a mixer and pulverized with a bead mill to obtain a slurry in which raw material powders were uniformly mixed.
- PVA polyvinyl alcohol
- the granulated powder was filled in a mold of a predetermined size and pressed at a surface pressure of 150 to 400 MPa for 1 to 3 minutes to obtain a molded body.
- the molded body is double vacuum packed with vinyl and CIP molded at 150 to 400 MPa, and then the molded body is heated to 1560 ° C. at a heating rate of 3 ° C./min, sintered at 1560 ° C. for 15 hours, and then in the furnace And left to cool.
- the density was 7.11 g / cm 3 .
- a sintered body having a size of about 1.5 cm square was cut out from the obtained sintered body, the cut surface was polished to a mirror surface, and the structure of the sintered body was observed with an electron microscope.
- the number of pores with an equivalent circle diameter of 0.1 ⁇ m or more existing in the range of an area of 80 ⁇ 120 ⁇ m 2 observed at a magnification of 1000 was 19 pieces.
- a square bar-shaped test piece is cut out from the sintered body, the surface is polished with a # 80 grindstone in the longitudinal direction of the test piece, and then polished with a # 400 grindstone in the longitudinal direction, and finally a width of 4 mm, Ten test pieces having a thickness of 3 mm and a length of 5 mm were produced.
- the surface roughness Ra was 0.46 ⁇ m.
- piece bending test was done according to the measuring method of JISR1601: 2008 except surface roughness Ra of a test piece.
- the average bending strength of 10 test pieces was 148 MPa.
- Example 2 A sintered body was produced under the same conditions as in Example 1 except that the sintering temperature was 1540 ° C.
- the Archimedes density of the sintered body was 7.11 g / cm 3 . Further, the structure of the sintered body was observed, and the number of pores having an equivalent circle diameter of 0.1 ⁇ m or more present in an area of 80 ⁇ 120 ⁇ m 2 observed at a magnification of 1000 was 28. Further, the surface roughness Ra of the bending strength test piece was 0.47 ⁇ m, and the average bending strength was 141 MPa.
- Example 1 A sintered body was produced under the same conditions as in Example 1 except that the sintering temperature was 1480 ° C.
- the Archimedes density of the sintered body was 7.09 g / cm 3 . Further, the structure of the sintered body was observed, and the number of pores with an equivalent circle diameter of 0.1 ⁇ m or more existing in an area of 80 ⁇ 120 ⁇ m 2 observed at a magnification of 1000 was 42. Further, the surface roughness Ra of the bending strength test piece was 0.45 ⁇ m, and the average bending strength was 128 MPa.
- Example 2 As a reference example, an example in which magnesium oxide is not added is shown.
- the raw material, indium oxide powder and tin oxide powder, were set to In: Sn 91.0: 9.0 in the atomic ratio, and granulated powder was produced using a normal method, under the same conditions as in Example 1.
- a sintered body was produced.
- the Archimedes density of the sintered body was 7.13 g / cm 3 . Further, the structure of the sintered body was observed, and the number of pores with an equivalent circle diameter of 0.1 ⁇ m or more existing in an area of 80 ⁇ 120 ⁇ m 2 observed at 1000 times magnification was 5.
- the surface roughness Ra of the bending strength test piece was 0.46 ⁇ m, and the average bending strength was 153 MPa.
- the present invention improves the reduction of the density and strength of the sintered body when magnesium oxide effective for making the film amorphous is added.
- the ITO sintered body does not contain magnesium oxide. It is not intended to improve the density and strength as compared with the above.
- the oxide sintered body of the present invention can form a Mg-containing ITO film excellent in amorphous stability and durability, and can provide a sputtering target with high bending strength. Sometimes target cracking and particle generation can be reduced.
- the thin film formed using the oxide sintered compact for sputtering targets of the present invention is particularly useful as a transparent conductive film in flat panel displays and flexible panel displays.
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Abstract
Description
1)実質的にインジウム、スズ、マグネシウム及び酸素からなり、スズがSn/(In+Sn+Mg)の原子数比で5~15%の割合、マグネシウムがMg/(In+Sn+Mg)の原子数比で0.1~2.0%の割合で含有されており、残部がインジウム及び酸素からなる焼結体であって、前記焼結体の表面粗さRaが0.3~0.5μmであるときの抗折強度が140MPa以上であることを特徴とする酸化物焼結体。
2)密度が7.1g/cm3以上であることを特徴とする請求項1記載の酸化物焼結体。
3)面積80×120μm2において、円相当径0.1μm以上のポアの数が30個以下であることを特徴とする請求項1又は2記載の酸化物焼結体。
原料粉末の混合が不十分であると、焼結工程において、反りやクラックの発生を招く恐れがあり、焼結体の密度も十分に上がらない。そして、そのような焼結体から製造されるターゲットをスパッタした場合、ノジュールの発生を招き、異常放電を引き起こす。さらに、ターゲットに酸化マグネシウムが偏析している高抵抗率領域と低抵抗率領域が存在することとなり、異常放電がさらに発生しやすくなる。
また、原料に酸化マグネシウムを用いない方法も実施されている。例えば、特許文献1の実施例には、マグネシウム原料として水酸化マグネシウムを用いており、特許文献2では、インジウム酸マグネシウム又はスズ酸マグネシウムを、特許文献6では、炭酸水酸化マグネシウムを用いている。
以上の方法に対して、後述する通り、本発明では、酸化スズ原料と酸化マグネシウム原料を混合・微粉砕してスラリーとし、別途、微粉砕してスラリーとした酸化インジウム原料と混合することにより、原料に酸化マグネシウムを用いても、高密度な焼結体を得ることを可能とした。
まず、酸化スズ及び酸化マグネシウムの所定量を秤量し、適量の純水を加えてミキサーを用いて充分な混合を行い、ビーズミルにより微粉砕しスラリーとする。また、同様に酸化インジウムを所定量秤量し、純水を加え混合・微粉砕を実施しスラリーを得る。
このとき、必要に応じ酸またはアルカリを用いてpH調整をしてスラリーの粘度を調整することができる。なお、原料粉は酸化物であるために雰囲気ガスは、特に原料の酸化を防止する等の考慮が必要ないために大気でもかまわない。
次に造粒を行う。これは、原料粉の流動性を良くして、プレス成型時の充填状況を充分良好なものにするためである。バインダーの役割を果たすPVA(ポリビニルアルコール)をスラリー1kgあたり100~200ccの割合で混合して、造粒機入口温度200~250℃、出口温度100~150℃、ディスク回転数8000~10000rpmの条件で造粒する。
次に、CIP成形を行う。上記で得られた成型体をビニールで2重に真空パックし、圧力150~400MPa、1~3分保持の条件でCIP(冷間等方圧加圧法)を施す。圧力150MPa未満であると、十分なCIPの効果を得ることができず、一方、400MPa以上の圧力を加えても、成形体の密度はある一定の値以上は向上しにくくなるため、400MPa以上の面圧は生産上特に必要とされない。
原料である酸化インジウム粉末、酸化スズ粉末及び酸化マグネシウム粉末を、原子数比でIn:Sn:Mg=90.5:9.0:0.5%となるように秤量し、まず、酸化スズ粉末と酸化マグネシウム粉末を混合した。次に、純水を加えて固形分30~50%のスラリーとし、アンモニアを適量加えてpH調整した後、ミキサーで混合し、ビーズミルによって微粉砕を実施した。混合・微粉砕後のスラリー中の原料粉の平均粒径(D50)は0.6μm以下とした。また別途、同様の方法により、所定量秤量した酸化インジウムに純水を加えてスラリーとし、混合・微粉砕を実施した。次に、酸化スズ及び酸化マグネシウムを混合したスラリーと、酸化インジウムのスラリーとをミキサーで混合し、ビーズミルにより微粉砕を行い、原料粉が均一に混合されたスラリーとした。次に、PVA(ポリビニルアルコール)をスラリー1kgあたり125ccの割合で混合して、造粒機入口温度220℃、出口温度120℃、ディスク回転数9000rpmの条件で造粒した。
焼結温度を1540℃とした以外は、実施例1と同じ条件で焼結体を作製した。焼結体のアルキメデス密度は、7.11g/cm3であった。また焼結体の組織観察を行い、倍率1000倍で観察した面積80×120μm2の範囲に存在する円相当径0.1μm以上のポアの数は28個であった。また、抗折強度試験片の表面粗さRaは0.47μmであり、平均抗折強度は141MPaであった。
焼結温度を1480℃とした以外は、実施例1と同じ条件で焼結体を作製した。焼結体のアルキメデス密度は、7.09g/cm3であった。また、焼結体の組織観察を行い、倍率1000倍で観察した面積80×120μm2の範囲に存在する円相当径0.1μm以上ポアの数は42個であった。また、抗折強度試験片の表面粗さRaは0.45μmであり、平均抗折強度は128MPaであった。
参考例として、酸化マグネシウムを添加しない例を示す。原料である酸化インジウム粉末、酸化スズ粉末を、原子数比でIn:Sn=91.0:9.0とし、通常の方法を用いて造粒粉を作製し、実施例1と同様の条件で焼結体を作製した。焼結体のアルキメデス密度は7.13g/cm3であった。また焼結体の組織観察を行い、倍率1000倍で観察した面積80×120μm2の範囲に存在する円相当径0.1μm以上ポアの数は5個であった。また、抗折強度試験片の表面粗さRaは0.46μmであり、平均抗折強度は153MPaであった。
ちなみに、本発明は、膜の非晶質化に有効な酸化マグネシウムを添加すると、焼結体の密度が下がり、強度が低下することを改善するものであり、酸化マグネシウムを含まないITO焼結体に比べて、密度や強度が向上するという趣旨のものではない。
Claims (3)
- 実質的にインジウム、スズ、マグネシウム及び酸素からなり、スズがSn/(In+Sn+Mg)の原子数比で5~15%の割合、マグネシウムがMg/(In+Sn+Mg)の原子数比で0.1~2.0%の割合で含有されており、残部がインジウム及び酸素からなる焼結体であって、前記焼結体の表面粗さRaが0.3~0.5μmであるときの抗折強度が140MPa以上であることを特徴とする酸化物焼結体。
- 密度が7.1g/cm3以上であることを特徴とする請求項1記載の酸化物焼結体。
- 面積80×120μm2において、円相当径0.1μm以上のポアの数が30個以下であることを特徴とする請求項1又は2記載の酸化物焼結体。
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KR20210129041A (ko) | 2019-02-18 | 2021-10-27 | 이데미쓰 고산 가부시키가이샤 | 산화물 소결체, 스퍼터링 타깃 및 스퍼터링 타깃의 제조 방법 |
WO2023162849A1 (ja) * | 2022-02-25 | 2023-08-31 | 株式会社アルバック | スパッタリングターゲット、スパッタリングターゲットの製造方法、酸化物半導体薄膜、薄膜半導体装置及びその製造方法 |
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