JP2007008780A - Manufacturing method of izo sputtering target - Google Patents
Manufacturing method of izo sputtering target Download PDFInfo
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- JP2007008780A JP2007008780A JP2005193504A JP2005193504A JP2007008780A JP 2007008780 A JP2007008780 A JP 2007008780A JP 2005193504 A JP2005193504 A JP 2005193504A JP 2005193504 A JP2005193504 A JP 2005193504A JP 2007008780 A JP2007008780 A JP 2007008780A
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 63
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000005245 sintering Methods 0.000 claims abstract description 28
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 24
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 238000010298 pulverizing process Methods 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 description 11
- 239000011324 bead Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 241000519995 Stachys sylvatica Species 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
本発明は、酸化インジウム及び酸化亜鉛又はこれらの粉末を主成分とするＩＺＯスパッタリングターゲットの製造方法に関する。 The present invention relates to a method for producing an IZO sputtering target mainly composed of indium oxide and zinc oxide or a powder thereof.
液晶表示装置やエレクトロルミネッセンス表示装置は、表示性能に優れ、かつ消費電力が少ないことから、携帯電話やパーソナルコンピュータ、ワードプロセッサ、テレビジョンなどの表示機器に広く用いられている。
これら表示機器に使用される透明導電膜としては、インジウムスズ酸化物（以下、ＩＴＯと略称する。）膜が主流を占めている。それは、このＩＴＯ膜が、光線透過率が高く、導電性に優れているほか、エッチング加工が可能であり、さらに基板との密着性にも優れているからである。通常、このＩＴＯ膜は、スパッタリング法やイオンプレーティング法、蒸着法によって製膜されている。
Liquid crystal display devices and electroluminescent display devices are widely used in display devices such as mobile phones, personal computers, word processors, and televisions because of their excellent display performance and low power consumption.
As the transparent conductive film used in these display devices, an indium tin oxide (hereinafter abbreviated as ITO) film dominates. This is because the ITO film has high light transmittance, excellent conductivity, etching processing, and excellent adhesion to the substrate. Usually, this ITO film is formed by sputtering, ion plating, or vapor deposition.
しかし、ＩＴＯは、上記の性質に関しては優れた性能を有するが、ＩＴＯのターゲットを用いて製膜された透明伝導膜は、そのエッチングに際して、王水や塩酸、臭化水素酸などの強酸を用いる必要があることから、薄膜型液晶表示装置における配線材料までエッチングされるという問題があった。
また、ＩＴＯは結晶性を有することから、エッチング加工に際し、透明導電膜の結晶粒の界面の部位からエッチングされる。これにより、透明導電膜のエッチング部位に、この結晶粒子が取り残され、表示素子とした場合に導通による表示不良の原因になるという問題もある。
However, ITO has excellent performance in terms of the above properties, but a transparent conductive film formed using an ITO target uses a strong acid such as aqua regia, hydrochloric acid, hydrobromic acid, etc. for etching. Since it is necessary, there is a problem that even the wiring material in the thin film type liquid crystal display device is etched.
In addition, since ITO has crystallinity, it is etched from the crystal grain interface portion of the transparent conductive film during the etching process. As a result, the crystal particles are left behind in the etched portion of the transparent conductive film, which causes a display defect due to conduction when used as a display element.
そこで、ＩＴＯ以外の組合せによる素材の検討がなされている。例えば酸化亜鉛と酸化錫を主原料としたもの、酸化錫にアンチモンを添加したもの、酸化亜鉛にアルミニウムを添加したもの、あるいは酸化インジウムと酸化亜鉛を主成分とするＩＺＯ等が提案されている（例えば、特許文献１、特許文献２参照）。中でも、酸化インジウムと酸化亜鉛を主成分とするＩＺＯは、ＩＴＯに比べてエッチング速度が大きいという特徴を有することから、注目を集めている。 In view of this, studies on materials using combinations other than ITO have been made. For example, a material mainly composed of zinc oxide and tin oxide, a material obtained by adding antimony to tin oxide, a material obtained by adding aluminum to zinc oxide, or IZO mainly composed of indium oxide and zinc oxide have been proposed ( For example, see Patent Document 1 and Patent Document 2). Among them, IZO, which contains indium oxide and zinc oxide as main components, has attracted attention because it has a feature that the etching rate is higher than that of ITO.
一般に、ＩＴＯスパッタリングターゲットは酸化インジウムおよび酸化亜鉛の粉末を混合、粉砕、乾燥、仮焼、粉砕、造粒、成型、焼結という多くの工程を経て製造されている（例えば、特許文献３参照）。このような多くの工程にわたるスパッタリングターゲットの製造は、生産性の低下を招き、コスト増になる要因となっているが、工程の削減などの改善は、十分に検討されていない。ＩＺＯスパッタリングターゲットの製造においても、前記のような従来通りの製造工程が踏襲され、工程の削減などの製造面での改善がなされていないのが現状であり、生産性の向上及び製造コストの低減が望まれている。 In general, an ITO sputtering target is manufactured through many steps of mixing, pulverizing, drying, calcining, pulverizing, granulating, molding, and sintering powders of indium oxide and zinc oxide (for example, see Patent Document 3). . The production of the sputtering target over many processes leads to a decrease in productivity and increases the cost, but improvement such as a reduction in the process has not been sufficiently studied. Even in the production of an IZO sputtering target, the conventional production process as described above has been followed, and there has been no improvement in production, such as a reduction in the production process. Is desired.
本発明は、このような状況の下で、ＩＺＯスパッタリングターゲットの製造において、ＩＺＯスパッタリングターゲットとしての特性を維持しつつ、工程を削減し、かつ焼結温度を下げることにより生産性の向上及び製造コストの低減が可能となる製造方法を提供することを目的とする。 Under such circumstances, the present invention improves productivity and reduces manufacturing costs by reducing the process and reducing the sintering temperature while maintaining the characteristics as an IZO sputtering target in the production of an IZO sputtering target. It is an object of the present invention to provide a manufacturing method that can reduce the above.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、特定の性状を有する酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末を用いることで、ＩＺＯスパッタリングターゲットとしての特性を維持しつつ、製造工程の削減し、かつ焼結温度を下げることが可能となることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the present inventors have used indium oxide powder and zinc oxide powder having specific properties, or raw material powders mainly composed of these powders. It has been found that the manufacturing process can be reduced and the sintering temperature can be lowered while maintaining the characteristics as an IZO sputtering target. The present invention has been completed based on such findings.
すなわち、本発明は、
（１）酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末を混合粉砕して微粉末を得る混合粉砕工程、前記微粉末を成型して成型物を得る成型工程、前記成型物を加圧下、酸素雰囲気中１１００〜１２５０℃で焼結して焼結体を得る焼結工程を含むことを特徴とするＩＺＯスパッタリングターゲットの製造方法であって、前記酸化インジウム粉末の比表面積が８〜１０ｍ2／ｇであり、前記酸化亜鉛粉末の比表面積が１０ｍ2／ｇ以上であるＩＺＯスパッタリングターゲットの製造方法、
（２）酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末を混合粉砕して微粉砕を得る混合粉砕工程、前記微粉末を成型して成型物を得る成型工程、前記成型物を加圧下、酸素雰囲気中１１００〜１２５０℃で焼結して焼結体を得る焼結工程を含むことを特徴とするＩＺＯスパッタリングターゲットの製造方法であって、前記酸化インジウム粉末の粒度分布のメジアン径が１〜２μｍであり、前記酸化亜鉛粉末の粒度分布のメジアン径が６５ｎｍ〜０．２μｍであり、前記混合粉砕工程後の平均メジアン径が０．５〜１μｍであるＩＺＯスパッタリングターゲットの製造方法、
（３）前記成型工程の前に、仮焼しないことを特徴とする上記（１）又は（２）に記載のＩＺＯスパッタリングターゲットの製造方法、及び
（４）前記焼結体の密度が６．５ｇ／ｃｍ3以上であることを特徴とする上記（１）〜（３）のいずれかに記載のＩＺＯスパッタリングターゲットの製造方法、
を提供するものである。
That is, the present invention
(1) A mixing and pulverizing step in which fine powder is obtained by mixing and pulverizing indium oxide powder and zinc oxide powder, or a raw material powder mainly composed of these powders, and a molding step in which the fine powder is molded to obtain a molded product A method for producing an IZO sputtering target, comprising a sintering step of obtaining a sintered body by sintering the molded product under pressure at 1100 to 1250 ° C. in an oxygen atmosphere. specific surface area of 8~10m 2 / g, a manufacturing method of the IZO sputtering target a specific surface area of 10 m 2 / g or more of the zinc oxide powder,
(2) A mixing and pulverizing step of mixing and pulverizing indium oxide powder and zinc oxide powder or raw powders mainly composed of these powders to obtain fine pulverization, and a molding step of forming the fine powder to obtain a molded product A method for producing an IZO sputtering target, comprising a sintering step of obtaining a sintered body by sintering the molded product under pressure at 1100 to 1250 ° C. in an oxygen atmosphere. IZO sputtering in which the median diameter of the particle size distribution is 1 to 2 μm, the median diameter of the particle size distribution of the zinc oxide powder is 65 nm to 0.2 μm, and the average median diameter after the mixing and grinding step is 0.5 to 1 μm Target manufacturing method,
(3) The method for producing an IZO sputtering target according to the above (1) or (2), which is not calcined before the molding step, and (4) a density of the sintered body is 6.5 g. a method of manufacturing the IZO sputtering target according to any one of the above (1) to (3), characterized in that at / cm 3 or more,
Is to provide.
本発明によれば、ＩＺＯスパッタリングターゲットの製造において、ＩＺＯスパッタリングターゲットとしての特性を維持しつつ、工程を削減し、かつ焼結温度を低くすることにより生産性の向上及び製造コストの低減が可能となる製造方法を提供することができる。 According to the present invention, in the production of an IZO sputtering target, it is possible to improve the productivity and reduce the manufacturing cost by reducing the process and reducing the sintering temperature while maintaining the characteristics as the IZO sputtering target. A manufacturing method can be provided.
［原料粉末］
本発明は、特定の性状を有する酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末を用いることで、製造工程の削減と焼結温度を低くすることを可能とするものである。
本発明で原料として用いる酸化インジウム粉末及び酸化亜鉛粉末の比表面積は、スパッタリングターゲット表面のホワイトスポット（白色斑点むら）と呼ばれる欠損の発現を低減するために、各々８〜１０ｍ2／ｇ及び１０ｍ2／ｇ以上であることを要する。
また、本発明で原料として用いる酸化インジウム粉末及び酸化亜鉛粉末の粒度分布のメジアン径は、ホワイトスポットの発現を低減するために、各々１〜２μｍ及び６５ｎｍ〜０．２μｍであることを要する。混合粉砕工程後の微粉末の平均メジアン径は、微細にするほど良いが、０．５〜１μｍとなるように粉砕する。この範囲内であれば、高密度のＩＺＯスパッタリングターゲットを得ることができ、粉砕時の粉砕機などからの不純物の混入量を低減させることが可能となる。なお、前記の原料となる粉末は、前記比表面積及びメジアン径を、両方満足することが好ましい。
[Raw material powder]
The present invention makes it possible to reduce the manufacturing process and lower the sintering temperature by using indium oxide powder and zinc oxide powder having specific properties or using raw material powders mainly composed of these powders. To do.
The specific surface area of the indium oxide powder and zinc oxide powder used as a raw material in the present invention, in order to reduce expression of defect called white spots of the sputtering target surface (white spots irregularities), each 8~10m 2 / g and 10 m 2 / G or more.
Moreover, the median diameters of the particle size distributions of the indium oxide powder and zinc oxide powder used as raw materials in the present invention are required to be 1 to 2 μm and 65 nm to 0.2 μm, respectively, in order to reduce the appearance of white spots. The average median diameter of the fine powder after the mixing and pulverizing step is preferably as fine as possible, but is pulverized to be 0.5 to 1 μm. Within this range, a high-density IZO sputtering target can be obtained, and the amount of impurities mixed from the pulverizer during pulverization can be reduced. In addition, it is preferable that the powder used as the raw material satisfies both the specific surface area and the median diameter.
前記酸化インジウム粉末と酸化亜鉛粉末の使用量は、重量比で７５：２５〜９５：５が好ましく、８０:２０〜９４：６がさらに好ましい。
本発明の製造にかかるＩＺＯスパッタリングターゲットの原料は、酸化インジウム及び酸化亜鉛を主成分とする限り、該ターゲットの特性を向上させる目的で、他の成分を添加してもよい。例えば、ＩＺＯスパッタリングターゲットのバルク電気抵抗値を低くするために、１００〜２０００ｐｐｍ程度の錫、ジルコニウム、チタン、ハフニウム、ゲルマニウム、セリウム等の正４価の元素を添加することができる。
The amount of the indium oxide powder and zinc oxide powder used is preferably 75:25 to 95: 5, and more preferably 80:20 to 94: 6, by weight.
As long as the raw material of the IZO sputtering target concerning manufacture of this invention has an indium oxide and a zinc oxide as a main component, you may add another component in order to improve the characteristic of this target. For example, a positive tetravalent element such as tin, zirconium, titanium, hafnium, germanium, cerium or the like can be added in an amount of about 100 to 2000 ppm in order to reduce the bulk electrical resistance value of the IZO sputtering target.
［製造方法］
ＩＺＯスパッタリングターゲットは、次のようにして製造される。酸化インジウム粉末と酸化亜鉛の粉末との、又はこれらの粉末を主成分とする混合物を湿式粉砕した微粉末を、スプレードライヤー等を用いて乾燥させた粒子をプレス成型し焼結した後、その成型物の焼結体に切削加工を施すことにより製造することができる。
混合粉砕工程とは、上記酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末は、湿式混合粉砕機、例えば湿式ボールミルやビーズミル、超音波などを用いて、均一に混合・粉砕して微粉末を得る工程である。粉砕した微粉末の粒径は、前記のようにＩＺＯスパッタリングターゲットの密度、及び粉砕時の粉砕機などからの不純物の混入量低減の観点より調整する。
ついで、得られた微粉末を乾燥させる。微粉末の乾燥には、スプレードライヤー、一般の粉末用乾燥機等を使用することができる。
乾燥した微粉末は、金型に充填して一般のコールドプレス機等を用いて所望の形状にプレス成型する成型工程を経る。プレス成型は、一軸プレス、冷間静水圧プレス（ＣＩＰ）等を用いてすることができる。
プレス成型して得られた成型物は、焼結工程を経て、ＩＺＯスパッタリングターゲット用焼結体となる。焼結は、酸素雰囲気下で行われる。酸素雰囲気とは、酸素濃度が２１％〜５０％未満、好ましくは２１％〜４０％未満であることをいう。この範囲内であれば、効率よく焼結することが可能であり、焼成炉が焼損することもない。なお、空気雰囲気でも焼結することもできる。また、焼結は、焼結密度を高くし、焼結炉を含めた焼結装置がコストアップしないようにする目的で、加圧下、大気圧超〜０．５ＭＰａで行われる。
焼結温度は１１００〜１２５０℃、好ましくは１１５０〜１２５０℃であり、この範囲内にあれば、焼結密度は高くなり、製造コストを低減することができる。焼結時間は焼結密度を高くし、製造コストを低減するために、２〜４８時間、好ましくは１０〜３６時間であり、焼結時の好ましい昇温速度は２〜２４℃／分である。
得られた成型物の焼結体からスパッタリングターゲットを製作するには、この焼結体をスパッタリング装置への装着に適した形状に切削加工して、これに装着用治具の取付をすればよい。この際、該ターゲットの平均表面粗さを向上させるために、鏡面加工をしてもよい。この鏡面加工には、化学研磨、機械研磨、化学機械研磨等の一般的な研磨方法を用いることができる。
[Production method]
The IZO sputtering target is manufactured as follows. Fine powder obtained by wet milling a mixture of indium oxide powder and zinc oxide powder, or a mixture containing these powders as a main component, press-sintered particles using a spray drier, etc., and then sintered. It can be manufactured by cutting a sintered body of the object.
The mixing and pulverizing step refers to the indium oxide powder and the zinc oxide powder, or the raw material powder containing these powders as a main component, uniformly using a wet mixing and pulverizing machine such as a wet ball mill, a bead mill, or an ultrasonic wave. This is a step of mixing and grinding to obtain fine powder. The particle size of the pulverized fine powder is adjusted from the viewpoint of reducing the density of the IZO sputtering target as described above and the amount of impurities mixed from the pulverizer during pulverization.
Next, the obtained fine powder is dried. For drying the fine powder, a spray dryer, a general powder dryer, or the like can be used.
The dried fine powder is subjected to a molding step of filling a mold and press-molding it into a desired shape using a general cold press machine or the like. The press molding can be performed using a uniaxial press, a cold isostatic press (CIP), or the like.
The molded product obtained by press molding becomes a sintered body for an IZO sputtering target through a sintering process. Sintering is performed in an oxygen atmosphere. The oxygen atmosphere means that the oxygen concentration is 21% to less than 50%, preferably 21% to less than 40%. If it is in this range, it is possible to sinter efficiently and the firing furnace will not burn out. Sintering can also be performed in an air atmosphere. In addition, the sintering is performed at a pressure exceeding atmospheric pressure to 0.5 MPa under pressure for the purpose of increasing the sintering density and preventing the cost of a sintering apparatus including a sintering furnace from increasing.
Sintering temperature is 1100-1250 degreeC, Preferably it is 1150-1250 degreeC, if it exists in this range, a sintering density will become high and manufacturing cost can be reduced. The sintering time is 2 to 48 hours, preferably 10 to 36 hours, in order to increase the sintered density and reduce the manufacturing cost, and the preferred temperature increase rate during sintering is 2 to 24 ° C./min. .
In order to produce a sputtering target from the sintered body of the obtained molded product, the sintered body is cut into a shape suitable for mounting on a sputtering apparatus, and a mounting jig is attached thereto. . At this time, mirror finishing may be performed to improve the average surface roughness of the target. For this mirror finishing, a general polishing method such as chemical polishing, mechanical polishing, chemical mechanical polishing, or the like can be used.
このように、特定の性状を有する酸化インジウム粉末と酸化亜鉛粉末とを、又はこれらの粉末を主成分とする原料粉末を用いることで、一般的にプレス成型による成型工程前に行っていた仮焼工程を経ることなく、また、焼結温度を低くしても、６．５ｇ／ｃｍ3以上の高密度を有するＩＺＯスパッタリングターゲット用焼結体を得ることができる。得られた焼結体を切削加工して製造したＩＺＯスパッタリングターゲットは、高密度であり、かつ該ターゲット表面にはホワイトスポット（白色斑点むら）と呼ばれる欠陥が存在しない優れた特性を有する。本発明の製造方法は、ＩＺＯスパッタリングターゲットの特性を維持しつつ、工程を削減し、かつ焼結温度を低くすることにより生産性の向上及び製造コストの低減が図れるものである。 Thus, by using indium oxide powder and zinc oxide powder having specific properties, or using raw material powders mainly composed of these powders, calcining generally performed before the molding process by press molding is performed. A sintered body for an IZO sputtering target having a high density of 6.5 g / cm 3 or more can be obtained without going through the steps and lowering the sintering temperature. The IZO sputtering target produced by cutting the obtained sintered body has a high density and has excellent characteristics in which defects called white spots (white spot unevenness) do not exist on the target surface. The manufacturing method of the present invention can improve productivity and reduce manufacturing costs by reducing the number of steps and lowering the sintering temperature while maintaining the characteristics of the IZO sputtering target.
本発明の製造方法により得られたＩＺＯスパッタリングターゲットは、上記のような特性を有することで、スパッタリング法により製膜する際にターゲット表面にノジュールと呼ばれる黒色の析出物（突起物）の発生を抑制する。従って、製膜速度の低下を招くことなく、異常放電で飛散したノジュールによる透明導電膜への異物混入を起こすこともないので、安定したスパッタを可能とし、また、膜特性に優れた透明伝導膜を得ることができる。 The IZO sputtering target obtained by the production method of the present invention has the above-described characteristics, thereby suppressing the occurrence of black precipitates (projections) called nodules on the target surface when the film is formed by the sputtering method. To do. Therefore, it does not cause a decrease in the film forming speed, and no nodule scattered by abnormal discharge does not cause foreign matter to be mixed into the transparent conductive film, thus enabling stable sputtering and excellent transparent film characteristics. Can be obtained.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、この例によってなんら限定されるものではない。
実施例１
比表面積が９ｍ2／ｇである酸化インジウム粉末９０重量部と比表面積が１２ｍ2／ｇである酸化亜鉛粉末１０重量部とを、湿式ビーズミルを用いて２４時間混合粉砕した。媒体には、１ｍｍφのジルコニアビーズを使用した。混合粉砕後、スプレードライヤーで乾燥させて得た微粉末を、金型に充填してコールドプレス及び冷間等方圧プレスを用いて１ｔ／ｃｍ2でプレス成型した。得られたられた成型物を、焼成炉に装入し、０．１５ＭＰａの加圧下において酸素濃度２５％の酸素雰囲気中１２３０℃で２４時間焼結した。得られたＩＺＯスパッタリングターゲット用焼結体は、仮焼工程が無いにもかかわらず、６．７２ｇ／ｃｍ3と高密度の焼結体であった。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
Example 1
90 parts by weight of indium oxide powder having a specific surface area of 9 m 2 / g and 10 parts by weight of zinc oxide powder having a specific surface area of 12 m 2 / g were mixed and ground using a wet bead mill for 24 hours. As the medium, 1 mmφ zirconia beads were used. After mixing and grinding, the fine powder obtained by drying with a spray dryer was filled in a mold and press-molded at 1 t / cm 2 using a cold press and a cold isostatic press. The obtained molded product was placed in a firing furnace and sintered at 1230 ° C. for 24 hours in an oxygen atmosphere having an oxygen concentration of 25% under a pressure of 0.15 MPa. The obtained sintered body for an IZO sputtering target was a sintered body having a high density of 6.72 g / cm 3 even though there was no calcining step.
実施例２
メジアン径が１．５μｍである酸化インジウム粉末９０重量部とメジアン径が０．１μｍである酸化亜鉛粉末１０重量部とを、湿式ビーズミルを用いて２４時間混合粉砕し、粉砕後のメジアン径を０．８μｍとした。媒体には、１ｍｍφのジルコニアビーズを使用した。混合粉砕後、スプレードライヤーで乾燥させて得た微粉末を、金型に充填してコールドプレス及び冷間等方圧プレスを用いて１ｔ／ｃｍ2でプレス成型した。得られた成型物を、焼成炉に装入し、０．１２ＭＰａの加圧下において酸素濃度３０％の酸素雰囲気中１１８０℃で２４時間焼結した。得られたＩＺＯスパッタリングターゲット用焼結体は、仮焼工程が無いにもかかわらず、６．６５ｇ／ｃｍ3と高密度の焼結体であった。
Example 2
90 parts by weight of indium oxide powder having a median diameter of 1.5 μm and 10 parts by weight of zinc oxide powder having a median diameter of 0.1 μm are mixed and ground for 24 hours using a wet bead mill, and the median diameter after grinding is reduced to 0. .8 μm. As the medium, 1 mmφ zirconia beads were used. After mixing and grinding, the fine powder obtained by drying with a spray dryer was filled in a mold and press-molded at 1 t / cm 2 using a cold press and a cold isostatic press. The obtained molded product was placed in a firing furnace and sintered at 1180 ° C. for 24 hours in an oxygen atmosphere with an oxygen concentration of 30% under a pressure of 0.12 MPa. The obtained sintered body for IZO sputtering target was a sintered body having a high density of 6.65 g / cm 3 , even though there was no calcining step.
比較例１
比表面積が９ｍ2／ｇである酸化インジウム粉末を９０重量部と比表面積が３ｍ2／ｇである酸化亜鉛粉末１０重量部とを、湿式ビーズミルを用いて２４時間混合粉砕した。媒体には、１ｍｍφのジルコニアビーズを使用した。混合粉砕後、スプレードライヤーで乾燥させて得た微粉末を、金型に充填してコールドプレス及び冷間等方圧プレスを用いて１ｔ／ｃｍ2でプレス成型した。得られた成型物を、焼成炉に装入し、空気雰囲気中で１４００℃、大気圧で２４時間焼結した。得られたＩＺＯスパッタリングターゲット用焼結体の密度は６．１０ｇ／ｃｍ3と低いものであった。
Comparative Example 1
90 parts by weight of indium oxide powder having a specific surface area of 9 m 2 / g and 10 parts by weight of zinc oxide powder having a specific surface area of 3 m 2 / g were mixed and ground using a wet bead mill for 24 hours. As the medium, 1 mmφ zirconia beads were used. After mixing and grinding, the fine powder obtained by drying with a spray dryer was filled in a mold and press-molded at 1 t / cm 2 using a cold press and a cold isostatic press. The obtained molded product was charged into a firing furnace and sintered in an air atmosphere at 1400 ° C. and atmospheric pressure for 24 hours. The density of the obtained sintered body for the IZO sputtering target was as low as 6.10 g / cm 3 .
比較例２
メジアン径が１．５μｍである酸化インジウム粉末９０重量部とメジアン径が１．０μｍである酸化亜鉛粉末１０重量部とを、湿式ビーズミルを用いて２４時間混合粉砕し、粉砕後のメジアン径を１．２μｍとした。媒体には、１ｍｍφのジルコニアビーズを使用した。混合粉砕後、スプレードライヤーで乾燥させて得た微粉末を、金型に充填してコールドプレス及び冷間等方圧プレスを用いて１ｔ／ｃｍ2でプレス成型した。得られた成型物を、焼成炉に装入し、空気雰囲気中で１２００℃、大気圧で２４時間焼結した。得られたＩＺＯスパッタリングターゲット用焼結体の密度は６．００ｇ／ｃｍ3と低いものであった。
Comparative Example 2
90 parts by weight of indium oxide powder having a median diameter of 1.5 μm and 10 parts by weight of zinc oxide powder having a median diameter of 1.0 μm are mixed and ground for 24 hours using a wet bead mill, and the median diameter after grinding is 1 .2 μm. As the medium, 1 mmφ zirconia beads were used. After mixing and grinding, the fine powder obtained by drying with a spray dryer was filled in a mold and press-molded at 1 t / cm 2 using a cold press and a cold isostatic press. The obtained molded product was placed in a firing furnace and sintered in an air atmosphere at 1200 ° C. and atmospheric pressure for 24 hours. The density of the obtained sintered body for the IZO sputtering target was as low as 6.00 g / cm 3 .
比較例３
比較例１及び比較例２において、混合粉砕後、かつプレス成型前に、空気雰囲気中１２００℃で仮焼を２時間行い、得られた仮焼粉末を湿式ビーズミルを用いて粉砕する以外は、比較例１及び比較例２と同様にしてＩＺＯスパッタリングターゲット用焼結体を得た。得られた焼結体の密度は、各々６．７３ｇ／ｃｍ3、６．７３ｇ／ｃｍ3と高くなった。前記密度の上昇は仮焼を行ったことによるものであり、実施例１及び実施例２よりも高密度の焼結体を得られたが、仮焼工程及び粉砕工程が追加されたことで生産性は低下した。
Comparative Example 3
In Comparative Example 1 and Comparative Example 2, after mixing and pulverizing and before press molding, calcination was performed at 1200 ° C. for 2 hours in an air atmosphere, and the obtained calcination powder was pulverized using a wet bead mill. In the same manner as in Example 1 and Comparative Example 2, a sintered body for an IZO sputtering target was obtained. The density of the obtained sintered body was as high as 6.73 g / cm 3 and 6.73 g / cm 3 , respectively. The increase in the density is due to calcination, and a sintered body having a higher density than those of Example 1 and Example 2 was obtained, but production was performed by adding a calcination step and a pulverization step. Sex declined.
本発明によれば、ＩＺＯスパッタリングターゲットの製造において、ＩＺＯスパッタリングターゲットとしての特性を維持しつつ、工程を削減し、かつ焼結温度を下げることにより生産性を向上させて、製造コストの低減を図ることができる。
According to the present invention, in the production of an IZO sputtering target, while maintaining the characteristics as an IZO sputtering target, the number of steps is reduced, and the productivity is improved by lowering the sintering temperature, thereby reducing the production cost. be able to.
Claims (4)
The density of the said sintered compact is 6.5 g / cm < 3 > or more, The manufacturing method of the IZO sputtering target in any one of Claims 1-3 characterized by the above-mentioned.
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| KR1020077030586A KR101317080B1 (en) | 2005-07-01 | 2006-06-27 | Process for producing izo sputtering target |
| CN201510104445.9A CN104710163A (en) | 2005-07-01 | 2006-06-27 | method for producing IZO sputtering target |
| PCT/JP2006/312825 WO2007004473A1 (en) | 2005-07-01 | 2006-06-27 | Process for producing izo sputtering target |
| TW095123888A TWI422699B (en) | 2005-07-01 | 2006-06-30 | IZO sputtering target manufacturing method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014029032A (en) * | 2007-12-13 | 2014-02-13 | Idemitsu Kosan Co Ltd | Sputtering target and method for manufacturing the same |
| KR20150045496A (en) | 2013-08-26 | 2015-04-28 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Sintered body and amorphous film |
| KR101600261B1 (en) | 2015-01-22 | 2016-03-09 | 제이엑스 킨조쿠 가부시키가이샤 | Oxide sintered compact, sputtering target and oxide thin film |
| KR20180081686A (en) | 2016-03-31 | 2018-07-17 | 제이엑스금속주식회사 | Indium zinc oxide (izo) based sputtering target, and method for producing same |
| CN116199496A (en) * | 2022-12-15 | 2023-06-02 | 先导薄膜材料（广东）有限公司 | Indium zinc oxide doped rare earth metal target material and preparation method thereof |
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| CN102191465A (en) * | 2010-03-18 | 2011-09-21 | 中国科学院福建物质结构研究所 | Indium-doped zinc oxide target material and preparation method of transparent conducting film |
| JP6078189B1 (en) * | 2016-03-31 | 2017-02-08 | Ｊｘ金属株式会社 | IZO sintered compact sputtering target and manufacturing method thereof |
| CN116162908A (en) * | 2022-12-15 | 2023-05-26 | 先导薄膜材料（广东）有限公司 | Indium zinc oxide target and preparation method thereof |
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| JP2002356767A (en) * | 2001-05-30 | 2002-12-13 | Nikko Materials Co Ltd | Method for manufacturing izo sputtering target |
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| JPH0570943A (en) * | 1991-09-11 | 1993-03-23 | Mitsubishi Materials Corp | High density sintered target material for forming electric conductive transparent thin film by sputtering |
| JPH0971860A (en) * | 1995-06-28 | 1997-03-18 | Idemitsu Kosan Co Ltd | Target and its production |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014029032A (en) * | 2007-12-13 | 2014-02-13 | Idemitsu Kosan Co Ltd | Sputtering target and method for manufacturing the same |
| KR20150045496A (en) | 2013-08-26 | 2015-04-28 | 제이엑스 닛코 닛세키 킨조쿠 가부시키가이샤 | Sintered body and amorphous film |
| KR101600261B1 (en) | 2015-01-22 | 2016-03-09 | 제이엑스 킨조쿠 가부시키가이샤 | Oxide sintered compact, sputtering target and oxide thin film |
| KR20180081686A (en) | 2016-03-31 | 2018-07-17 | 제이엑스금속주식회사 | Indium zinc oxide (izo) based sputtering target, and method for producing same |
| KR20190019104A (en) | 2016-03-31 | 2019-02-26 | 제이엑스금속주식회사 | Indium zinc oxide (izo) based sputtering target, and method for producing same |
| KR20200019654A (en) | 2016-03-31 | 2020-02-24 | 제이엑스금속주식회사 | Indium zinc oxide (izo) based sputtering target, and method for producing same |
| CN116199496A (en) * | 2022-12-15 | 2023-06-02 | 先导薄膜材料（广东）有限公司 | Indium zinc oxide doped rare earth metal target material and preparation method thereof |
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