JP5892016B2 - Zinc oxide sputtering target and manufacturing method thereof - Google Patents
Zinc oxide sputtering target and manufacturing method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 110
- 239000011787 zinc oxide Substances 0.000 title claims description 51
- 238000005477 sputtering target Methods 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000005245 sintering Methods 0.000 claims description 45
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 29
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000010304 firing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 description 24
- 239000013077 target material Substances 0.000 description 24
- 239000010408 film Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- 239000002019 doping agent Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 238000004544 sputter deposition Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
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- 229920003145 methacrylic acid copolymer Polymers 0.000 description 3
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 argon ions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
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- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
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- 238000001704 evaporation Methods 0.000 description 1
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- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Description
本発明は、太陽電池等を構成する透明導電膜をスパッタリング法にて形成する際に用いられる酸化亜鉛スパッタリングターゲットに係り、特に、ＣＩＧＳ系太陽電池のバッファ層に用いられる高抵抗膜（酸化物透明半導体膜）をスパッタリング法により効率良く成膜できる酸化亜鉛スパッタリングターゲットの改良に関するものである。 The present invention relates to a zinc oxide sputtering target used when forming a transparent conductive film constituting a solar cell or the like by a sputtering method, and in particular, a high resistance film (transparent oxide) used for a buffer layer of a CIGS solar cell. The present invention relates to an improvement in a zinc oxide sputtering target capable of efficiently forming a semiconductor film by a sputtering method.
酸化物透明導電膜（酸化物透明導体膜若しくは半導体膜）は、導電性と可視光領域での高い透過率を有するため、太陽電池や液晶表示素子、その他各種受光素子の電極等に利用され、更に、近赤外線領域の波長での反射吸収特性を生かして、自動車や建築物の窓ガラス若しくはフィルム等に用いる熱線反射膜や各種の帯電防止膜、冷凍ショーケース等の防曇用の透明発熱体としても利用されている。 An oxide transparent conductive film (oxide transparent conductive film or semiconductor film) has high conductivity in the visible light region, and is used for electrodes of solar cells, liquid crystal display elements, and other various light receiving elements. Furthermore, taking advantage of the reflection and absorption characteristics at wavelengths in the near-infrared region, transparent heating elements for anti-fogging, such as heat ray reflective films, various antistatic films, refrigeration showcases, etc., used for window glass or films of automobiles and buildings, etc. It is also used as.
これ等酸化物透明導電膜（酸化物透明導体膜若しくは半導体膜）が利用される分野の中で、ＣＩＧＳ系太陽電池に用いられる酸化物透明導電膜の中には適度な絶縁抵抗が求められる用途がある。これは、ＣＩＧＳ系太陽電池の発電層から電気を取り出す導電膜層（透明電極層）との間に、電荷の移動（漏れ出し）を妨げる層（バッファ層）を設けることにより発電効率を向上させるためである。当初はＣｄＳやＺｎＳが上記バッファ層に用いられていたが、薄膜太陽電池の表面電極には一般的に酸化亜鉛系の透明電極が用いられており、環境面、積層のし易さ等から、バッファ層においても酸化亜鉛系の透明導電膜（酸化物透明半導体膜）が用いられるようになっている。 Among the fields where these oxide transparent conductive films (oxide transparent conductive films or semiconductor films) are used, the oxide transparent conductive films used for CIGS solar cells are required to have appropriate insulation resistance. There is. This improves power generation efficiency by providing a layer (buffer layer) that prevents the movement (leakage) of charges between the conductive layer (transparent electrode layer) that extracts electricity from the power generation layer of the CIGS solar cell. Because. Initially, CdS and ZnS were used for the buffer layer, but a zinc oxide-based transparent electrode is generally used for the surface electrode of the thin-film solar cell. Also in the buffer layer, a zinc oxide-based transparent conductive film (oxide transparent semiconductor film) is used.
これ等酸化物透明導電膜の形成方法としては、真空中で蒸発源を加熱し、蒸発した原料を基板上に堆積させて形成する真空蒸着法、ターゲットにアルゴンイオンを衝突させてターゲットを構成する物質をたたき出し、対向する基板に堆積させて形成するスパッタリング法、および、透明導電層形成用塗液を塗布して形成する方法等が用いられている。この中で、真空蒸着法やスパッタリング法は、蒸気圧の低い材料を使用する際や精密な膜厚制御を必要とする際に有効な手法であり、かつ、操作が非常に簡便であるため工業的に広く利用されており、特に、スパッタリング法は、短時間に効率良く薄膜を形成できることから最も広く利用されている。 As a method for forming these oxide transparent conductive films, a vacuum evaporation method in which an evaporation source is heated in vacuum and evaporated materials are deposited on a substrate, and a target is formed by colliding argon ions with a target. A sputtering method in which a substance is knocked out and deposited on an opposing substrate, a method in which a transparent conductive layer forming coating solution is applied, and the like are used. Among these, the vacuum deposition method and the sputtering method are effective methods when using a material having a low vapor pressure or when precise film thickness control is required, and the operation is very simple. In particular, the sputtering method is most widely used because a thin film can be efficiently formed in a short time.
このスパッタリングターゲット材（焼結体）には、長時間安定したスパッタリング成膜が行なえるようにするため、相対密度で、少なくとも９０％を越える高い密度が求められる。ここで、上記「相対密度」とは、ターゲット材の出発原料である各混合粉末の真密度から求めた計算真密度に対する焼結体（ターゲット材）の密度の比率（％）のことで、（上記焼結体の密度／計算真密度）×１００＝焼結体の相対密度（％）という式により求められる値である。尚、計算真密度は、ＡＺＯ（アルミニウムをドーパントとして含む酸化亜鉛系のターゲット材）であれば、計算真密度＝１００／［（酸化亜鉛の配合比(質量％)／酸化亜鉛の真密度）＋（酸化アルミニウムの配合比(質量％)／酸化アルミニウムの真密度）］で計算される。 The sputtering target material (sintered body) is required to have a high relative density of at least 90% so that stable sputtering film formation can be performed for a long time. Here, the “relative density” is a ratio (%) of the density of the sintered body (target material) to the calculated true density obtained from the true density of each mixed powder that is a starting material of the target material. It is a value obtained by the formula: density of the sintered body / calculated true density) × 100 = relative density (%) of the sintered body. If the calculated true density is AZO (a zinc oxide-based target material containing aluminum as a dopant), the calculated true density = 100 / [(compounding ratio of zinc oxide (mass%) / true density of zinc oxide) + (Aluminum oxide mixing ratio (mass%) / true density of aluminum oxide)].
相対密度の高い焼結体を得るためには、ホットプレス法や熱間静水圧プレス法等が試みられているが、生産性の点から常圧焼結法が多く採用されている。常圧焼結を行なうための成形体を得る方法として、原料粉をスラリーにして鋳込む方式と、粉体をプレスして成形を行なう方式が取られるが、平板形状のターゲットを作製するにはプレス成形での生産が適している。 In order to obtain a sintered body having a high relative density, a hot pressing method, a hot isostatic pressing method, and the like have been tried, but an atmospheric pressure sintering method is often employed from the viewpoint of productivity. There are two methods for obtaining compacts for atmospheric pressure sintering: casting the raw material powder into a slurry and pressing the powder for molding. Production by press molding is suitable.
また、スパッタリング方式には様々な駆動方式があるが、最も量産性に優れるのはＤＣマグネトロンスパッタ方式であり、これに適用可能なスパッタリングターゲットには、一定程度以上の導電性が必要である。しかし、ドーパント量が少ない（例えば、ドーパントの添加量が０．０１〜０．１質量％）酸化亜鉛系ターゲットでは、導電性を高めるためにドーパントの添加量を増加するに従い焼結体の密度が低下するという問題があった（特許文献１参照）。 Further, there are various driving methods in the sputtering method, but the DC magnetron sputtering method is most excellent in mass productivity, and a sputtering target applicable to this requires a certain level of conductivity. However, in a zinc oxide target with a small amount of dopant (for example, 0.01 to 0.1% by mass of dopant), the density of the sintered body increases as the amount of dopant added is increased in order to increase conductivity. There has been a problem of reduction (see Patent Document 1).
すなわち、０．１質量％以下の酸化アルミニウムを含有する（すなわち、ドーパント量の少ない）酸化亜鉛系ターゲットでは、特許文献１の表１（段落００３５）に記載されているように、上記ドーパント（Ａｌ2Ｏ3）の添加量を増加する（０．００質量％〜０．１０質量％）に従い、密度が５．３０〜５．０２ｇ／ｃｍ3と低下している。酸化亜鉛の真密度は５．７８ｇ／ｃｍ3、酸化アルミニウムの真密度は３．９９ｇ／ｃｍ3であるので、酸化アルミニウムが０．００質量％〜０．１０質量％のときの計算真密度は、上述の計算式から約５．７８ｇ／ｃｍ3となり、相対密度は９２％以下のものしか得られていない。 That is, in the zinc oxide target containing 0.1% by mass or less of aluminum oxide (that is, having a small amount of dopant), as described in Table 1 (paragraph 0035) of Patent Document 1, the dopant (Al The density decreases from 5.30 to 5.02 g / cm 3 as the addition amount of ( 2 O 3 ) increases (0.00 mass% to 0.10 mass%). Since the true density of zinc oxide is 5.78 g / cm 3 and the true density of aluminum oxide is 3.99 g / cm 3 , the calculated true density when the aluminum oxide is 0.00 mass% to 0.10 mass% is From the above formula, it is about 5.78 g / cm 3 , and a relative density of only 92% or less is obtained.
他方、透明電極等に広く用いられている２〜５質量％の酸化アルミを含有する（すなわち、ドーパント量の多い）酸化亜鉛系ターゲットでは、特許文献１に引用された特開平７−２５８８３６号公報の段落００２５と段落００３５に記載されているように、酸化アルミニウムの含有量が２質量％で密度が５．６１ｇ／ｃｍ3以上、すなわち、相対密度が９８％以上と高いものが得られ、市販されている。 On the other hand, in a zinc oxide-based target containing 2 to 5% by mass of aluminum oxide (that is, having a large amount of dopant) widely used for transparent electrodes and the like, Japanese Patent Laid-Open No. 7-258836 cited in Patent Document 1 is disclosed. As described in paragraphs 0025 and 0035, the aluminum oxide content is 2% by mass and the density is not less than 5.61 g / cm 3 , that is, the relative density is as high as 98% or more. Has been.
このため、ＣＩＧＳ系太陽電池のバッファ層にドーパント量の少ない酸化亜鉛系ターゲット（相対密度が９２％以下）を適用し、かつ、ＣＩＧＳ系太陽電池の導電膜層（透明電極層）にドーパント量の多い酸化亜鉛系ターゲット（相対密度が９８％以上）を適用した場合、形成される導電膜層（透明電極層）とバッファ層との間に大きな密度差が生じてしまうため、生産効率を大きく損ねてしまう課題（問題点）が存在した。 For this reason, a zinc oxide type target (relative density is 92% or less) with a small amount of dopant is applied to the buffer layer of the CIGS solar cell, and the amount of dopant is applied to the conductive layer (transparent electrode layer) of the CIGS solar cell. When a large amount of zinc oxide-based target (relative density is 98% or more) is applied, a large density difference occurs between the formed conductive film layer (transparent electrode layer) and the buffer layer. There was a problem (problem) that would occur.
本発明はこのような問題点に着目してなされたもので、その課題とするところは、ドーパントである酸化アルミニウムの添加量が０．１０質量％以下と少量にも拘らず、相対密度が９５％以上である酸化亜鉛スパッタリングターゲットとその製造方法を提供することにある。 The present invention has been made paying attention to such problems, and the problem is that the relative density is 95 despite the small amount of aluminum oxide as a dopant being 0.10% by mass or less. It is in providing the zinc oxide sputtering target which is% or more, and its manufacturing method.
すなわち、請求項１に係る発明は、
酸化亜鉛スパッタリングターゲットにおいて、
酸化亜鉛を主成分とし、０．０５質量％以上０．１０質量％以下の酸化アルミニウムを含有する酸化物焼結体で構成され、かつ、酸化物焼結体の相対密度が９５％以上であることを特徴とする。
That is, the invention according to claim 1
In zinc oxide sputtering target,
It is composed of an oxide sintered body containing zinc oxide as a main component and containing 0.05% by mass or more and 0.10% by mass or less of aluminum oxide, and the relative density of the oxide sintered body is 95% or more. It is characterized by that.
また、請求項２に係る発明は、
請求項１に記載の酸化亜鉛スパッタリングターゲットを製造する方法において、
酸化亜鉛粉末と酸化アルミニウム粉末を、純水、有機バインダー、分散剤と混合してスラリーを調製し、かつ、得られたスラリーを、乾燥、造粒する第一工程と、
第一工程で得られた造粒粉を、加圧成形して成形体を得る第二工程と、
第二工程で得られた成形体を焼成し、酸化物焼結体を得る第三工程と、
を備え、
上記第三工程における焼結温度を９００〜１１５０℃の範囲とし、４０〜６０時間焼成することを特徴とする。
The invention according to claim 2
In the method of manufacturing the zinc oxide sputtering target according to claim 1 ,
A zinc oxide powder and an aluminum oxide powder are mixed with pure water, an organic binder, a dispersant to prepare a slurry, and the obtained slurry is dried and granulated,
A second step in which the granulated powder obtained in the first step is pressed to obtain a molded body;
A third step of firing the molded body obtained in the second step to obtain an oxide sintered body,
With
The sintering temperature in the third step is set to a range of 900 to 1150 ° C., and firing is performed for 40 to 60 hours.
本発明に係る酸化亜鉛スパッタリングターゲットによれば、ドーパントである酸化アルミニウムの添加量が０．０５質量％以上０．１０質量％以下と少量であるにも拘らず、酸化アルミニウムの添加量が２〜５質量％と多量である市販の酸化亜鉛スパッタリングターゲットと同様にその相対密度が９５％以上の高い値になっている。 According to the zinc oxide sputtering target according to the present invention, although the addition amount of aluminum oxide as a dopant is as small as 0.05% by mass or more and 0.10% by mass or less , the addition amount of aluminum oxide is 2 to 2. Similar to a commercially available zinc oxide sputtering target having a large amount of 5% by mass, the relative density is as high as 95% or more.
このため、本発明に係る酸化亜鉛スパッタリングターゲットを例えばＣＩＧＳ系太陽電池のバッファ層に適用した場合、酸化アルミニウムの添加量が２〜５質量％と多量である市販の酸化亜鉛スパッタリングターゲットを用いて形成された導電膜層（透明電極層）との間に大きな密度差が生じないことから、積層効率が著しく向上して大幅な生産性の向上が図れる効果を有している。 For this reason, when the zinc oxide sputtering target according to the present invention is applied to, for example, a buffer layer of a CIGS solar cell, it is formed using a commercially available zinc oxide sputtering target in which the amount of aluminum oxide added is as large as 2 to 5% by mass. Since a large density difference does not occur with the conductive film layer (transparent electrode layer) formed, there is an effect that the stacking efficiency is remarkably improved and the productivity is greatly improved.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明に係る酸化亜鉛スパッタリングターゲットは、酸化亜鉛粉末を主とし、０．０５質量％以上０．１０質量％以下の酸化アルミニウム粉末を含有する金属酸化物粉末に、水と有機バインダーと分散剤とを混合してスラリーを調製し、かつ、得られたスラリーを噴霧し、乾燥させて造粒粉を得る第一工程と、得られた造粒粉を加圧成形して成形体を得る第二工程と、得られた成形体を焼成して焼結体を得る第三工程と、得られた焼結体を機械加工してスパッタリングターゲットを得る工程を経て製造される。 The zinc oxide sputtering target according to the present invention is mainly composed of zinc oxide powder, metal oxide powder containing 0.05% by mass or more and 0.10% by mass or less of aluminum oxide powder, water, an organic binder, and a dispersant. A first step of preparing a slurry by spraying the obtained slurry and drying to obtain a granulated powder, and a second step of obtaining a molded body by press-molding the obtained granulated powder. It is manufactured through a step, a third step of firing the obtained molded body to obtain a sintered body, and a step of machining the obtained sintered body to obtain a sputtering target.
出発原料として、ＢＥＴ比表面積が４ｍ2／ｇである酸化亜鉛粉末に、ＢＥＴ比表面積が６ｍ2／ｇである酸化アルミニウム粉末を添加し、分散剤として、分散能力に優れるアクリル酸メタクリル酸共重合体アンモニア中和物を用いると、酸化亜鉛粉末の凝集が効果的に抑えられ、均一なスラリーを得ることができるため好ましい。上記分散剤の添加量は、酸化アルミニウム粉末を含む金属酸化物粉末の合計質量に対して０．３〜３質量％とすることが好ましい。添加量を０．３〜３質量％とすることにより、スラリーの濃度が７０質量％程度であっても、スラリーの粘度は１００ｃｐｓ未満となり、噴霧、乾燥工程における噴霧が容易となる。また、上記分散剤の添加により、金属酸化粉末の沈降も抑えられるため、噴霧、乾燥工程における効率が著しく向上することとなる。上記分散剤の添加量を０．３質量％未満にすると、分散能力が不十分となる可能性がある。上記分散剤を使用しない場合には、濃度が３０〜３５質量％程度のスラリーであっても、粘度が１００ｃｐｓ以上になってしまい、噴霧、乾燥工程における噴霧が行い難くなる。一方、上記分散剤の添加量が３質量％を越えると、焼結時に揮発分が多くなるため、焼結時に製品が割れる確率が高くなってしまう。 As a starting material, the zinc oxide powder has a BET specific surface area of 4m 2 / g, a BET specific surface area was added to the aluminum oxide powder is 6 m 2 / g, as a dispersant, methacrylic acrylate acid copolycondensation of excellent dispersing ability Use of a combined ammonia neutralized product is preferable because aggregation of zinc oxide powder is effectively suppressed and a uniform slurry can be obtained. The amount of the dispersant added is preferably 0.3 to 3% by mass with respect to the total mass of the metal oxide powder including the aluminum oxide powder. By setting the addition amount to 0.3 to 3% by mass, even if the concentration of the slurry is about 70% by mass, the viscosity of the slurry becomes less than 100 cps, and spraying in the spraying and drying process becomes easy. Moreover, since the precipitation of the metal oxide powder is suppressed by the addition of the dispersant, the efficiency in the spraying and drying process is remarkably improved. If the added amount of the dispersing agent is less than 0.3% by mass, the dispersing ability may be insufficient. When the dispersant is not used, even if the slurry has a concentration of about 30 to 35% by mass, the viscosity becomes 100 cps or more, and spraying in the spraying and drying process becomes difficult. On the other hand, if the added amount of the dispersant exceeds 3% by mass, the volatile content increases during sintering, and the probability that the product breaks during sintering will increase.
分散剤としてアクリル酸メタクリル酸共重合体アンモニア中和物を用いた場合には分散能力が非常に高くなるので、加える有機バインダーはポリビニルアルコール（ＰＶＡ）で十分であり、成形体は十分な強度が得られる。用いるＰＶＡは、ケン化度９０〜９７ｍｏｌ％、重合度４００〜１０００のものが適している。この範囲のケン化度と重合度のＰＶＡを用いることにより、得られる造粒粉は適度に軟質なものとなり、成形時のつぶれ性が向上する。この結果、成形体中の空孔が減少し、成形体強度が向上し、焼成して得られるスパッタリングターゲットの密度が向上する。ケン化度が９７ｍｏｌ％を越えるか、重合度が１０００を越えるＰＶＡを用いると、成形時の造粒粉のつぶれ性が悪くなり、成形体中の空孔が増加し、成形体強度が減少する。また、焼結後に得られるスパッタリングターゲットの密度も向上しない。一方、ケン化度が９０ｍｏｌ％未満であるか、重合度が４００未満であるＰＶＡを用いると、成形体が軟質となり過ぎ、作業効率が悪くなる。尚、本発明においては、有機バインダーとしてＰＶＡを用いれば十分であるが、ＰＶＡの他、アクリル系バインダー等を用いることも可能である。有機バインダーの量は、通常、１．０質量％以上を加えることにより成形体強度を確保するが、本発明で得ようとする焼結体の厚みが１０ｍｍ以上であることから、有機バインダーを１．０質量％以下としても成形体強度の低下は顕著に現れず、成形以後の工程で割れる確率が高くなることはない。このため、酸化アルミニウム粉末を含む金属酸化物粉末の合計質量に対して０．５〜１．５質量％とすることが好ましい。また、ジルコニアボールを用いたボールミルまたはビーズミルを行うことにより、金属酸化物粉末を充分に混合しておくことが望ましい。 When an acrylic acid / methacrylic acid copolymer ammonia neutralized product is used as a dispersant, the dispersibility is very high. Therefore, polyvinyl alcohol (PVA) is sufficient as the organic binder to be added, and the molded product has sufficient strength. can get. As the PVA to be used, those having a saponification degree of 90 to 97 mol% and a polymerization degree of 400 to 1000 are suitable. By using PVA having a saponification degree and a polymerization degree within this range, the resulting granulated powder becomes moderately soft and the crushability during molding is improved. As a result, voids in the molded body are reduced, the molded body strength is improved, and the density of the sputtering target obtained by firing is improved. When PVA with a saponification degree exceeding 97 mol% or a polymerization degree exceeding 1000 is used, the collapsibility of the granulated powder at the time of molding deteriorates, voids in the molded body increase, and the molded body strength decreases. . Moreover, the density of the sputtering target obtained after sintering is not improved. On the other hand, when PVA having a saponification degree of less than 90 mol% or a polymerization degree of less than 400 is used, the molded article becomes too soft and the working efficiency is deteriorated. In the present invention, it is sufficient to use PVA as the organic binder, but it is also possible to use an acrylic binder or the like in addition to PVA. The amount of the organic binder is usually 1.0% by mass or more to ensure the strength of the molded body, but since the thickness of the sintered body to be obtained in the present invention is 10 mm or more, the organic binder is 1 Even if the content is less than 0.0% by mass, the reduction in the strength of the molded product does not appear remarkably and the probability of cracking in the steps after molding does not increase. For this reason, it is preferable to set it as 0.5-1.5 mass% with respect to the total mass of the metal oxide powder containing an aluminum oxide powder. Further, it is desirable that the metal oxide powder is sufficiently mixed by performing ball milling or bead milling using zirconia balls.
酸化亜鉛粉末、酸化アルミニウム粉末、アクリル酸メタクリル酸共重合体アンモニア中和物およびＰＶＡを水に加え、充分に混合させて得たスラリーを、噴霧し、乾燥させて造粒粉を作製する場合、乾燥温度を１３０〜２００℃にすることが好ましい。乾燥温度を１３０℃未満にすると、造粒粉の水分量が多くなり、成形体強度が低くなる。一方、乾燥温度が２００℃を越えると、造粒粉が硬質となり、成形時に空孔が生じ易くなり、スパッタリングターゲットの密度が向上し難くなる。 When a slurry obtained by adding zinc oxide powder, aluminum oxide powder, acrylic acid / methacrylic acid copolymer ammonia neutralized product and PVA to water and mixing well, and spraying to dry to produce granulated powder, The drying temperature is preferably 130 to 200 ° C. When the drying temperature is less than 130 ° C., the moisture content of the granulated powder increases, and the strength of the molded body decreases. On the other hand, when the drying temperature exceeds 200 ° C., the granulated powder becomes hard, and voids are likely to occur during molding, and the density of the sputtering target is difficult to improve.
平板状の成形体を得るには、例えば、特開２００６−１９３７９７号に記載されているような耐久性に優れたアメゴムから成る筒状ゴム型と、成形体が食い込み難く、滑りが良いシリコンゴムから成る２枚の板状ゴム型とで構成される成形型を用い、この成形型内に、造粒粉を充填し、冷間静水圧プレスを行なって、上記成形体を得ることができる。 In order to obtain a flat molded body, for example, a cylindrical rubber mold made of candy rubber having excellent durability as described in JP-A-2006-19397, and a silicon rubber that does not easily bite into the molded body and has good sliding properties. The molded body can be obtained by using a molding die composed of two plate-like rubber dies composed of the above, filling the molding die with granulated powder, and performing cold isostatic pressing.
冷間静水圧プレスの成形圧力は、１００〜３００ＭＰａとすることが好ましい。成形圧力を１００ＭＰａ未満にすると、成形体密度および成形体強度が低下し、製品歩留りが悪くなる。一方、成形圧力が３００ＭＰａを越えても、成形体密度および成形体強度に対する効果はほとんど変化しない。 The forming pressure of the cold isostatic press is preferably 100 to 300 MPa. When the molding pressure is less than 100 MPa, the density of the molded body and the strength of the molded body are lowered, and the product yield is deteriorated. On the other hand, even if the molding pressure exceeds 300 MPa, the effect on the compact density and the compact strength hardly changes.
上記成形体を焼結する際の焼結温度は、酸化亜鉛粉末の粒成長が期待できる９００℃以上とすることが好ましい。しかし、焼結温度が１１５０℃を越えると、空孔が内部に取り残されるため好ましくない。また、焼結時間が１５時間を越えると揮発や表面の反応が進むため好ましくないとされていたが、焼結最高温度を１１５０℃以下に抑えることにより４０時間を越える焼結時間を行うことができる。 The sintering temperature at the time of sintering the molded body is preferably 900 ° C. or higher at which grain growth of the zinc oxide powder can be expected. However, if the sintering temperature exceeds 1150 ° C., voids are left inside, which is not preferable. In addition, if the sintering time exceeds 15 hours, volatilization and surface reaction proceed, which is not preferable. However, by suppressing the maximum sintering temperature to 1150 ° C. or less, the sintering time exceeding 40 hours can be performed. it can.
以下、本発明の実施例について具体的に説明する。 Examples of the present invention will be specifically described below.
［実施例１］
平均粒径が１μｍ以下の酸化亜鉛粉末と、平均粒径が１μｍ以下の酸化アルミニウム粉末を、酸化アルミニウム粉末の含有量が０．０５質量％となるように混合した原料粉末に、水、１質量％のＰＶＡバインダー、０．５質量％のアクリル酸メタクリル酸共重合体アンモニア中和物から成る分散剤を添加し、ビーズミル（アシザワ・ファインテック株式会社製：ＬＭＺ型）にて混合してスラリーを調製した。
[Example 1]
A raw material powder obtained by mixing a zinc oxide powder having an average particle diameter of 1 μm or less and an aluminum oxide powder having an average particle diameter of 1 μm or less so that the content of the aluminum oxide powder is 0.05 mass%, water, 1 mass % Of PVA binder, 0.5% by weight of acrylic acid / methacrylic acid copolymer neutralized ammonia, and a slurry is prepared by mixing with a bead mill (manufactured by Ashizawa Finetech Co., Ltd .: LMZ type). Prepared.
得られたスラリーを、スプレードライヤー（大川原化工機株式会社製：ＯＤＬ−２０型）を用い、供給速度１４０ｍｌ／ｍｉｎ、熱風温度１４０℃、熱風量８Ｎｍ３／ｍｉｎの条件で乾燥造粒して、酸化アルミニウムの含有量が０．０５質量％である酸化亜鉛と酸化アルミニウムから成る造粒粉を得た。 The obtained slurry was dried and granulated using a spray dryer (Okawara Kako Co., Ltd .: ODL-20 type) at a supply rate of 140 ml / min, a hot air temperature of 140 ° C., and a hot air amount of 8 Nm 3 / min. A granulated powder composed of zinc oxide and aluminum oxide having an aluminum oxide content of 0.05% by mass was obtained.
次に、上述した筒状ゴム型と２枚の板状ゴム型とで構成される成形型に上記造粒粉を充填し、冷間静水圧プレス（株式会社神戸製鋼製）にて３００ＭＰａで成形し、長さ２５０ｍｍ、幅１５０ｍｍ、厚さ１０ｍｍの成形体を得た。 Next, the above-mentioned granulated powder is filled in a molding die composed of the above-described cylindrical rubber die and two plate-like rubber dies, and is molded at 300 MPa with a cold isostatic press (manufactured by Kobe Steel Co., Ltd.). Thus, a molded body having a length of 250 mm, a width of 150 mm, and a thickness of 10 mm was obtained.
得られた成形体を、焼結炉（丸祥電器株式会社製）に入れ、大気中にて０．５℃／分の速度で６００℃まで昇温し、０．３℃／分の速度で６００〜１０００℃の温度範囲を昇温した。その後、１０００℃にて４０時間、焼結した後、室温まで冷却し、長さ２１７ｍｍ、幅１３０ｍｍ、厚み９ｍｍの焼結体を得た。 The obtained molded body is put into a sintering furnace (manufactured by Marusho Denki Co., Ltd.), heated to 600 ° C. at a rate of 0.5 ° C./min in the atmosphere, and at a rate of 0.3 ° C./min. The temperature range of 600-1000 ° C. was raised. Then, after sintering at 1000 degreeC for 40 hours, it cooled to room temperature and obtained the sintered compact of length 217mm, width 130mm, and thickness 9mm.
そして、焼結体の上下面、側面の加工を行い、２１０ｍｍ×１２５ｍｍ×７ｍｍの酸化亜鉛スパッタリングターゲット材を得た。 Then, the upper and lower surfaces and side surfaces of the sintered body were processed to obtain a 210 mm × 125 mm × 7 mm zinc oxide sputtering target material.
更に、長さ、幅をノギスで測定し、厚みをマイクロメーターで測定し、電子天秤で重量を測定して密度計算を行い、相対密度に換算した。 Further, the length and width were measured with calipers, the thickness was measured with a micrometer, the weight was measured with an electronic balance, the density was calculated, and the relative density was converted.
すなわち、実測値から求めた焼結体の密度は５．５６ｇ／ｃｍ3、計算真密度は５．７８ｇ／ｃｍ3であり、相対密度は９６．２％であった。 That is, the density of the sintered body determined from the actually measured values was 5.56 g / cm 3 , the calculated true density was 5.78 g / cm 3 , and the relative density was 96.2%.
この結果を表１に示す。 The results are shown in Table 1.
［実施例２〜３］
焼結保持温度が１１５０℃である点を除き実施例１と同様にして（実施例２）、また、焼結保持温度が９００℃かつ焼結保持時間が６０時間である点を除き実施例１と同様にして（実施例３）、実施例２〜３に係る酸化亜鉛スパッタリングターゲット材を得た。
[Examples 2-3]
Example 1 except that the sintering holding temperature is 1150 ° C. (Example 2), except that the sintering holding temperature is 900 ° C. and the sintering holding time is 60 hours. In the same manner (Example 3), the zinc oxide sputtering target material according to Examples 2-3 was obtained.
更に、実施例１と同様の方法により実施例２〜３に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target material according to Examples 2-3 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［参考例４〜６］
酸化アルミニウムの配合量（含有量）が０質量％である点を除き実施例１〜３と同様にして参考例４〜６に係る酸化亜鉛スパッタリングターゲット材を得た。
[ Reference Examples 4 to 6]
Zinc oxide sputtering target materials according to Reference Examples 4 to 6 were obtained in the same manner as in Examples 1 to 3 except that the blending amount (content) of aluminum oxide was 0% by mass.
更に、実施例１と同様の方法により参考例４〜６に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target materials according to Reference Examples 4 to 6 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［実施例７〜９］
酸化アルミニウムの配合量（含有量）が０．１０質量％である点を除き実施例１〜３と同様にして実施例７〜９に係る酸化亜鉛スパッタリングターゲット材を得た。
[Examples 7 to 9]
Zinc oxide sputtering target materials according to Examples 7 to 9 were obtained in the same manner as in Examples 1 to 3 except that the blending amount (content) of aluminum oxide was 0.10% by mass.
更に、実施例１と同様の方法により実施例７〜９に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target material according to Examples 7 to 9 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［比較例１〜３］
焼結保持温度が１２００℃である点を除き実施例１と同様にして（比較例１）、また、焼結保持温度が１２００℃かつ焼結保持時間が２０時間である点を除き実施例１と同様にして（比較例２）、更に、焼結保持温度が８００℃かつ焼結保持時間が６０時間である点を除き実施例１と同様にして（比較例３）、比較例１〜３に係る酸化亜鉛スパッタリングターゲット材を得た。
[Comparative Examples 1-3]
Example 1 except that the sintering holding temperature is 1200 ° C. (Comparative Example 1), except that the sintering holding temperature is 1200 ° C. and the sintering holding time is 20 hours. (Comparative Example 2) and Comparative Example 1 to Comparative Example 1 except that the sintering holding temperature is 800 ° C. and the sintering holding time is 60 hours (Comparative Example 3). The zinc oxide sputtering target material which concerns on this was obtained.
更に、実施例１と同様の方法により比較例１〜３に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target materials according to Comparative Examples 1 to 3 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［比較例４〜６］
酸化アルミニウムの配合量（含有量）が０質量％で焼結保持温度が１２００℃である点を除き実施例１と同様にして（比較例４）、また、酸化アルミニウムの配合量（含有量）が０質量％で焼結保持温度が１２００℃かつ焼結保持時間が２０時間である点を除き実施例１と同様にして（比較例５）、更に、酸化アルミニウムの配合量（含有量）が０質量％で焼結保持温度が８００℃かつ焼結保持時間が６０時間である点を除き実施例１と同様にして（比較例６）、比較例４〜６に係る酸化亜鉛スパッタリングターゲット材を得た。
[Comparative Examples 4 to 6]
Similar to Example 1 (Comparative Example 4) except that the blending amount (content) of aluminum oxide is 0% by mass and the sintering holding temperature is 1200 ° C., and the blending amount (content) of aluminum oxide. In the same manner as in Example 1 except that the sintering holding temperature is 1200 ° C. and the sintering holding time is 20 hours (Comparative Example 5). Further, the blending amount (content) of aluminum oxide is A zinc oxide sputtering target material according to Comparative Examples 4 to 6 was prepared in the same manner as in Example 1 (Comparative Example 6) except that the sintering holding temperature was 0 mass%, the sintering holding temperature was 800 ° C., and the sintering holding time was 60 hours. Obtained.
更に、実施例１と同様の方法により比較例４〜６に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target materials according to Comparative Examples 4 to 6 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［比較例７〜９］
酸化アルミニウムの配合量（含有量）が０．１０質量％で焼結保持温度が１２００℃である点を除き実施例１と同様にして（比較例７）、酸化アルミニウムの配合量（含有量）が０．１０質量％で焼結保持温度が１２００℃かつ焼結保持時間が２０時間である点を除き実施例１と同様にして（比較例８）、酸化アルミニウムの配合量（含有量）が０．１０質量％で焼結保持温度が８００℃かつ焼結保持時間が６０時間である点を除き実施例１と同様にして（比較例９）、比較例７〜９に係る酸化亜鉛スパッタリングターゲット材を得た。
[Comparative Examples 7 to 9]
The amount (content) of aluminum oxide was the same as that of Example 1 (Comparative Example 7) except that the amount (content) of aluminum oxide was 0.10% by mass and the sintering retention temperature was 1200 ° C. Is the same as Example 1 (Comparative Example 8) except that the sintering holding temperature is 1200 ° C. and the sintering holding time is 20 hours, and the blending amount (content) of aluminum oxide is Zinc oxide sputtering target according to Comparative Examples 7 to 9 in the same manner as Example 1 (Comparative Example 9) except that the sintering holding temperature is 0.10% by mass, the sintering holding temperature is 800 ° C., and the sintering holding time is 60 hours. The material was obtained.
更に、実施例１と同様の方法により比較例７〜９に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target materials according to Comparative Examples 7 to 9 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
［比較例１０］
焼結保持時間が３０時間である点を除き実施例８と同様にして、比較例１０に係る酸化亜鉛スパッタリングターゲット材を得た。
[Comparative Example 10]
A zinc oxide sputtering target material according to Comparative Example 10 was obtained in the same manner as in Example 8 except that the sintering holding time was 30 hours.
更に、実施例１と同様の方法により比較例１０に係る酸化亜鉛スパッタリングターゲット材の相対密度を求めた。 Furthermore, the relative density of the zinc oxide sputtering target material according to Comparative Example 10 was determined by the same method as in Example 1.
この結果も表１に示す。 The results are also shown in Table 1.
「確 認」
（１）酸化亜鉛を主成分とし、０．１０質量％以下の酸化アルミニウムを含有する酸化亜鉛スパッタリングターゲット材を製造する際、第三工程の焼結温度（焼結保持温度）が９００〜１１５０℃、焼成時間（保持時間）が４０〜６０時間の常圧焼結条件を満たすことにより、相対密度９５％以上の酸化亜鉛スパッタリングターゲット材を製造できることが実施例１〜３、参考例４〜６、および、実施例７〜９により確認される。
"Confirmation"
(1) When manufacturing a zinc oxide sputtering target material containing zinc oxide as a main component and containing 0.10% by mass or less of aluminum oxide, the sintering temperature (sintering holding temperature) in the third step is 900 to 1150 ° C. Examples 1-3 and Reference Examples 4-6 that a zinc oxide sputtering target material having a relative density of 95% or more can be produced by satisfying the atmospheric pressure sintering condition with a firing time (holding time) of 40-60 hours . And it is confirmed by Examples 7-9 .
（２）他方、上記酸化亜鉛スパッタリングターゲット材を製造する際、第三工程の焼結温度（焼結保持温度）が８００℃以下または１２００℃以上の場合（すなわち、９００〜１１５０℃の条件を満たさない場合）は、焼成時間（保持時間）が４０〜６０時間の常圧焼結条件を満たしたとしても、相対密度９５％以上の酸化亜鉛スパッタリングターゲット材が得られないことが比較例１〜９により確認される。 (2) On the other hand, when manufacturing the said zinc oxide sputtering target material, when the sintering temperature (sintering holding temperature) of a 3rd process is 800 degrees C or less or 1200 degrees C or more (namely, the conditions of 900-1150 degreeC are satisfy | filled. Comparative Example 1-9 that a zinc oxide sputtering target material having a relative density of 95% or more cannot be obtained even when the sintering time (holding time) satisfies the atmospheric pressure sintering conditions of 40 to 60 hours. Is confirmed.
（３）更に、上記酸化亜鉛スパッタリングターゲット材を製造する際、第三工程における焼結温度（焼結保持温度）の条件（９００〜１１５０℃）を満たしたとしても、焼成時間（保持時間）の条件（４０〜６０時間）を満たさない場合には、相対密度９５％以上の酸化亜鉛スパッタリングターゲット材が得られないことが比較例１０により確認される。 (3) Furthermore, when manufacturing the said zinc oxide sputtering target material, even if the conditions (900-1150 degreeC) of the sintering temperature (sintering holding temperature) in a 3rd process are satisfy | filled, baking time (holding time) When the conditions (40 to 60 hours) are not satisfied, it is confirmed by Comparative Example 10 that a zinc oxide sputtering target material having a relative density of 95% or more cannot be obtained.
本発明に係る酸化亜鉛スパッタリングターゲットによれば、ドーパントである酸化アルミニウムの添加量が０．１０質量％以下と少量にも拘らず相対密度が９５％以上の高い値になっているため、ＣＩＧＳ系太陽電池におけるバッファ層の形成に適用できる産業上の利用可能性を有している。 According to the zinc oxide sputtering target according to the present invention, since the additive amount of aluminum oxide as a dopant is 0.10% by mass or less and the relative density is a high value of 95% or more, the CIGS type is high. It has industrial applicability applicable to the formation of buffer layers in solar cells.
Claims (2)
酸化亜鉛粉末と酸化アルミニウム粉末を、純水、有機バインダー、分散剤と混合してスラリーを調製し、かつ、得られたスラリーを、乾燥、造粒する第一工程と、
第一工程で得られた造粒粉を、加圧成形して成形体を得る第二工程と、
第二工程で得られた成形体を焼成し、酸化物焼結体を得る第三工程と、
を備え、
上記第三工程における焼結温度を９００〜１１５０℃の範囲とし、４０〜６０時間焼成することを特徴とする酸化亜鉛スパッタリングターゲットの製造方法。 In the method of manufacturing the zinc oxide sputtering target according to claim 1 ,
A zinc oxide powder and an aluminum oxide powder are mixed with pure water, an organic binder, a dispersant to prepare a slurry, and the obtained slurry is dried and granulated,
A second step in which the granulated powder obtained in the first step is pressed to obtain a molded body;
A third step of firing the molded body obtained in the second step to obtain an oxide sintered body,
With
A method for producing a zinc oxide sputtering target, wherein the sintering temperature in the third step is in the range of 900 to 1150 ° C., and firing is performed for 40 to 60 hours.
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