CN103221572A - 制造高密度氧化锡铟(ito)溅射靶 - Google Patents
制造高密度氧化锡铟(ito)溅射靶 Download PDFInfo
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- CN103221572A CN103221572A CN201180038918XA CN201180038918A CN103221572A CN 103221572 A CN103221572 A CN 103221572A CN 201180038918X A CN201180038918X A CN 201180038918XA CN 201180038918 A CN201180038918 A CN 201180038918A CN 103221572 A CN103221572 A CN 103221572A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000005477 sputtering target Methods 0.000 title abstract description 10
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000000843 powder Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 60
- 238000005245 sintering Methods 0.000 claims abstract description 44
- 150000001875 compounds Chemical group 0.000 claims description 25
- 229910052714 tellurium Inorganic materials 0.000 claims description 15
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 15
- 238000007582 slurry-cast process Methods 0.000 claims description 12
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 10
- 229910052787 antimony Inorganic materials 0.000 claims description 10
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- 229910052797 bismuth Inorganic materials 0.000 claims description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 10
- 229910052711 selenium Inorganic materials 0.000 claims description 10
- 239000011669 selenium Substances 0.000 claims description 10
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 9
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 9
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- WPYVAWXEWQSOGY-UHFFFAOYSA-N indium antimonide Chemical compound [Sb]#[In] WPYVAWXEWQSOGY-UHFFFAOYSA-N 0.000 claims description 5
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 5
- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
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- 239000002253 acid Substances 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- JRIGVWDKYXCHMG-UHFFFAOYSA-N (5-arsoroso-2-hydroxyphenyl)azanium;chloride Chemical compound Cl.NC1=CC([As]=O)=CC=C1O JRIGVWDKYXCHMG-UHFFFAOYSA-N 0.000 claims description 2
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 claims description 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 2
- 229960002594 arsenic trioxide Drugs 0.000 claims description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052738 indium Inorganic materials 0.000 abstract description 9
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- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 abstract 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 60
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 26
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- MEEBXICQJZFZGI-UHFFFAOYSA-K [B+3].O.[PH2](=O)[O-].[PH2](=O)[O-].[PH2](=O)[O-] Chemical compound [B+3].O.[PH2](=O)[O-].[PH2](=O)[O-].[PH2](=O)[O-] MEEBXICQJZFZGI-UHFFFAOYSA-K 0.000 description 1
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- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
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- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
提供了制造氧化锡铟(ITO)溅射靶的方法。所述方法包括:沉淀氢氧化铟和氢氧化锡、煅烧氢氧化物、以生产颗粒状ITO粉末、使用添加剂(如专门的烧结助剂、分散剂和粘结剂)制备ITO粉末的含水浆液、研磨浆液以得到粉浆、使用多孔铸模通过浇注粉浆制备压实的ITO生坯或干燥粉浆以产生颗粒状ITO粉末和冷等静压粉末、和烧结生坯以产生具有大于理论的99%的高密度的ITO靶。
Description
技术领域
本发明涉及制造氧化锡铟(ITO)溅射靶的方法。尤其是,本发明涉及压实ITO粉末,然后烧结,以得到高密度ITO靶。
背景技术
在光谱的可见光范围中,ITO呈现光学和电传输性质的显著的组合:(i)高电导率(≈104Ω-1cm-1)和(ii)高光学透明度(>85%)。这使得ITO为透明的导电氧化物(TCO),在玻璃和塑料片材上其薄膜是光学透明的,同时,提供高电导率。这形成ITO在平板显示器如液晶显示器(LCD)和光生伏打太阳能电池板中的应用的基础,其中,ITO用作透明的导电体或电极。ITO的另外的吸引人的性质在于其薄膜稳定并且长时间保持它们的性质。
在现有技术中,ITO为用于制造显示器和太阳能电池用透明电极的标准主流TCO材料。在现有技术方法中:(i)将ITO形成为溅射靶,其然后用于在玻璃或塑料片材上溅射薄膜(≈2μm厚),和(ii)对于显示器电路,使用化学平板印刷方法通过蚀刻将ITO膜转化为透明的线路,而对于太阳能电池,直接使用而没有蚀刻作为均匀的平面顶部电极。溅射的方法为通过在高真空中通过等离子体携带的离子轰击从ITO靶(阴极)除去材料,以及在玻璃片材(阳极)上沉积的过程,如图1所示。
工业标准溅射方法需要ITO溅射靶,其为具有金属灰色外观的高密度ITO材料的矩形成型体。通常,ITO靶制造过程包括:(i)通过精炼制造高纯度5N铟和锡金属,(ii)生产5N ITO粉末,(iii)生产含有添加剂的ITO浆液,(iv)使用机械研磨将ITO浆液转化为粉浆,(v)通过浇注或压制生产ITO生坯(术语‘生坯’表示预先烧制的陶瓷体),和(vi)通过在加热炉中烧制,烧结ITO生坯,以生产高密度的ITO靶(参见图2)。在烧结的最终过程中,生坯中的颗粒融合,以得到较大的颗粒,从而提高密度。伴随着生坯的显著收缩。
在现有技术中已知,在ITO生坯中存在杂质可增强烧结过程。在压实之前将这些杂质特意加入到ITO粉末中,它们称为‘烧结助剂’。常见的烧结助剂包括硅和稀土金属的氧化物。然而,ITO为难以烧结的材料,并且在现有技术中引用的常见的烧结剂不能充分增强烧结,以高生产率生产具有大于理论密度的99%的均匀密度的大ITO靶。巨大的挑战在于如TFT-LCD工业所需要的那些实现跨越靶表面大于理论的99%的ITO靶密度。
为了得到满意的溅射和具有足以用于LCD相关的应用(尤其是基于薄膜晶体管(TFT)的LCD)的品质的ITO薄膜,高和均匀的密度的ITO靶是非常重要的,其中,ITO靶尺寸要求大,为≥250cm2。
如果靶密度不大于理论的99%并且不均匀,则在ITO溅射过程期间会遇到问题。在溅射过程中,靶经历高密度功率,这也导致高表面温度。在TFT-LCD生产过程中实现在经济上可行的薄膜沉积速率,需要高密度。高表面温度意味着在使用期间ITO靶需要冷却。通过使矩形ITO靶的一面与铜板粘结能实现这一点。铜板也用于向ITO靶施加电压和在靶上实现高密度功率。将铜板在金属块上向下栓螺栓,该金属块在铜板下面具有中央空腔,并且水循环通过该空腔。铜板用作从ITO靶提取热量的散热器,因此防止靶被熔融。
本领域技术人员将理解,如果跨越靶的密度不高并且不均匀,则存在跨越靶表面溅射速率的不均匀性,导致在靶表面上的品质缺陷,如热点(hotspot)和瘤状物。进而,这些可导致在ITO薄膜中的品质缺陷。
因此,本领域技术人员已经知道,跨越大的靶表面实现高的和均匀的密度是头等重要的。本领域技术人员还已知理论密度需要大于99%的密度。跨越大ITO靶均匀实现这种高密度的挑战在于,ITO为难以烧结的材料。为了成功的均匀烧结,需要ITO生坯中的颗粒晶界融合,导致提高颗粒尺寸和伴随密度提高的生坯的显著收缩。
在现有技术中,已进行以下显著的努力:(1)实现具有均匀的和最佳的生密度的大的ITO生坯,和(2)开发用于实现满意的生坯烧结的方法。
在现有技术的一种方法中,通过加压模制法如热等静压(HIP)(US6099982;US6123787)或冷等静压(CIP)(US5531948),通过模塑ITO粉末制备ITO生坯。在HIP中,ITO粉末在高压力和高温度下成型,因此引起烧结,以产生高密度的烧结的ITO坯体。在冷等静压方法中,通过冷压将ITO粉末铸造成成型体,然后在1400-1750℃范围的高温加热炉中烧制成型体,以产生高密度的烧结的ITO靶。
在现有技术的另一种方法中,通过称为无压粉浆浇注的方法制备ITO生坯。然后将这些在高温下在加热炉中烧制,以实现烧结。在一种粉浆浇注方法中(JP1117136/88;JP117137/88;JP117138/88),将氧化铟和氧化锡在液体如水中与分散剂和粘合剂混合,然后使用机械研磨方法研磨,以得到称为“粉浆”的浆液,将其注入由石膏或熟石膏制成的吸水性多孔铸模中。然后将铸模中的浆液随着水经由铸模孔隙离开铸模而缓慢干燥。所使用的分散剂例如选自聚羧酸,粘合剂例如选自丙烯酸类乳液。在此方法中,在50-200kPa范围的压力下将粉浆注入铸模中。通过采用不低于100MPa压力的压力使生坯经历冷等静压来进一步增加生坯密度的。然后在1300-1400℃下烧结ITO靶,以获得密度大于95%的高密度靶。然而,该现有技术存在密度大于99%的靶的产率低的问题。另外,在填充石膏或熟石膏铸模期间,铸模材料可进入粉浆或粘附于ITO“生坯”块,导致靶被铸模材料污染。接着,这些杂质导致ITO薄膜电导率的降低以及溅射过程中的问题例如瘤状物的形成。
在另一种方法中(JP2005324987),为了在制造期间制备生坯然后烧结和避免使用粉浆浇注铸模,将氧化铟和氧化锡粉末、水和有机粘结剂混合,研磨,然后喷雾至干燥以产生颗粒状的粉末,然后以高压压塑,以产生生坯。将后者烧结以产生高密度的ITO靶。
在现有技术的另一个实施方案中(JP10330926),调整靶的密度以实现大于或等于99%,还将存在于烧结的靶中空隙的最大直径调整至小于或等于10微米,而在靶的1mm2面积内少于1000个空隙。这是通过氧化铟和氧化锡的共沉淀,然后在含有卤化氢如氯化氢或卤素气体如氯的气氛中煅烧氧化物来实现的。接着通过粉浆浇注并烧制生坯将粉末模制成压实生坯。在此方式中,能获得密度大于或等于99%和尺寸大于100cm2的靶。然而,由于该方法使用高度有毒而且不稳定的气体而非常危险。
现有技术的上述方法使用硅或钇或锆的氧化物作为烧结助剂。通过在颗粒晶界处引入不稳定性的这些功能促进颗粒晶界的分解和熔融。然而,如前所述,ITO为难以烧结的材料,并且在现有技术中已知的烧结助剂不足以能够以高生产率制造具有高和均匀密度的大尺寸ITO靶。
发明内容
本发明的目的是提供容易实现的高和均匀密度的方法,优选大于理论的99%,特别是在用于高应用效率的大尺寸的靶(优选≥250cm2)中,特别是在LCD相关的溅射应用中。
该目标是通过包括以下(至少在优选实施方案中)的方法来得到:由酸性溶液(如盐酸或硝酸溶液)共沉淀氧化铟和氧化锡,过滤,洗涤和煅烧氧化物,制备具有添加剂如分散剂、粘结剂、基于砷、锑、铋、硒、碲和/或硼的化合物的专门的烧结助剂的氧化物的含水浆液,研磨该浆液以得到合适的粒径分布和颗粒表面积的“粉浆”,在特定的糖类和螯合剂涂覆的熟石膏多孔铸模中使用粉浆浇注来压实浆液或在多孔塑料铸模中在高达40bar的压力下加压粉浆浇注,然后在氧气氛中烧结所得到的压实的ITO生坯,以产生黑灰色的高密度(大于或等于理论密度的99%)ITO靶。
根据本发明的一方面,提供了生产用于在制造ITO溅射靶中使用的颗粒状ITO粉末的方法。在空气中煅烧氢氧化铟和氢氧化锡粉末的均匀混合物。煅烧可以在800℃-1200℃范围内、更优选1000℃的温度下实施。所得到的颗粒状ITO粉末用于制造ITO靶。
根据本发明的另一方面,提供了形成用于在制造ITO溅射靶中使用的ITO粉浆的方法。形成含有颗粒状ITO粉末、水和添加剂的浆液。添加剂包括在浆液中浓度为0.001%-1%重量百分比的硼、砷、锑、铋、硒或碲的化合物或它们的混合物。浆液然后经历机械研磨,以产生ITO粉浆。这些元素的化合物不限于可为它们的氧化物、酸或它们与铟的化合物如锑化铟、砷化铟、硒化铟或碲化铟。在烧结期间,这些硼、砷、锑、铋、硒、碲化合物与ITO生坯中的氧化铟相互作用,并且形成化合物,如锑化铟、砷化铟、硒化铟、碲化铟。这些铟化合物在低于ITO的烧结温度的温度下形成玻璃状液相。在ITO颗粒晶界处存在这些液相促进ITO颗粒熔融,导致增强的烧结、较大的颗粒和较高的密度。另外,砷、锑、铋、硒和碲的这些化合物可与粉浆中的其它添加剂如硅酸盐相互作用,以形成玻璃状硅酸盐化合物,在低于烧结温度下也为液相,并且还可促进ITO颗粒晶界的熔融。在此方式中,这些化合物在烧结过程中充当ITO烧结助剂和高密度促进剂,容易导致在ITO靶中大于99%的较高密度。
根据本发明,用于制备粉浆的颗粒状ITO粉末优选包含表面积为1-5m2/g的氧化铟(III)和氧化锡(IV)。氧化物以>75%重量范围的浓度存在于粉浆中。粉浆还可含有粘结剂(如丙烯酸类乳液)和/或分散剂(如聚羧酸)和常见的烧结助剂(如二氧化硅)。
然后通过注入多孔铸模将粉浆进行粉浆浇注,并放置在环境温度下,以形成“生坯”。接着将生坯干燥,然后在氧气中以>1400℃的高温烧制,以实现烧结。在此阶段中,在ITO颗粒晶界处作为玻璃状液相存在的烧结助剂促进烧结,导致在靶中大颗粒和高密度。
根据本发明的另一方面,提供了制造ITO溅射靶的方法。石膏或熟石膏的多孔铸模涂布有糖类或淀粉脱模剂的层。然后在0.1-45psi的压力下将ITO粉浆注入该铸模中。
备选地,可在高达10Mpa的高压力下将粉浆注入多孔聚合物铸模中,并且粉浆浇注。
将生坯在50℃下干燥几天,然后在氧气中在约1000℃-1700℃温度下烧制。
可以理解的是,本发明的各方面可以组合。
附图说明
图1示意性说明溅射过程;
图2说明包括在制造ITO靶中的步骤的流程图。
具体实施方式
为了可以完全理解本发明并容易将本发明投入实际效果中,现在将通过非限制性的实例仅描述本发明优选的实施方案。
在对现有技术和在用于TFT-LCD应用的大尺寸靶中实现高和均匀的密度的问题深入细致的研究后,本发明人通过不使用现有技术的危险气体如氯化氢或氯气、也不需要冷等静压来实现高的均匀的密度,成功地开发了基于新的烧结助剂的方法,该方法可容易得到具有>99%密度的大的靶。
通过克服例如在溅射期间瘤状物形成、靶破裂、跨越靶体的不均匀性质以及异常放电的问题,该改进的方法能够生产≥250cm2的大尺寸ITO溅射靶,其得到适合于TFT-LCD工业的品质的ITO薄膜并提供高的靶应用率。
生产含有氧化铟(III)和氧化锡(IV)的ITO靶,其氧化铟(III)含量不低于75%重量百分比。而且,允许除了铟和锡的氧化物以外第三成分的存在,以达到高的和均匀的靶密度,同时使靶破裂最小化。这种第三成分优选包含硼、砷、锑、铋、硒和/或碲的化合物。
在该过程的第一阶段,在氯化物介质中沉淀氧化铟和氧化锡,过滤,洗涤,和在800-1200℃下煅烧。将表面积在1-5m2/g范围,优选4m2/g的所得到的颗粒状氧化铟和氧化锡粉末使用水制成浆液,使得氧化物的浓度不低于75%重量百分比,更优选在75-85%范围。浆液还含有浓度为ITO粉末干基质量的0.1-2%的分散剂(例如聚羧酸)和浓度为ITO粉末干基质量的0.1-5%的粘结剂(例如丙烯酸类乳液),但是不具体局限于这些化合物。浆液另外含有硼、砷、锑、铋、硒和/或碲的化合物或它们的混合物。这种化合物可包括这些元素的相应的氧化物或酸或它们与铟的化合物,如砷化铟、锑化铟、硒化铟和碲化铟。这些化合物在浆液中的浓度在所用的ITO粉末干基质量的0.001%-1%范围。浆液还可含有在所用的ITO粉末干基质量的0.001%-1%范围的常见的烧结助剂,如二氧化硅。
通过使用珠磨机、盘磨机或球磨机机械研磨,将浆液转变为适用于粉浆浇注的粉浆。将研磨进行到ITO颗粒达到这样的粒径分布:粒径在50-800nm的范围内且表面积在7.5-9.5m2/g范围。这种粉浆的粘度为通过使用以25rpm的轴转速的轴65的布氏流变仪所测量的500-1400cps的范围内。
然后将得到的粉浆通过0.5微米的过滤器过滤,接着注入由例如石膏、熟石膏或多孔聚合物的材料制成的多孔铸模。其中,石膏或熟石膏用作铸模材料,铸模涂布有一薄层脱模剂如糖类或淀粉。在环境温度下放置填充后的铸模。通过经由多孔铸模的水吸收作用诱导的毛细管力将浆液材料压实成高密度的形状的生坯。
在高达10Mpa的高压力下,可将粉浆注入固定在工业加压粉浆浇注机中的多孔聚合物铸模中。在10-40分钟的浇注时间后,将铸模打开,并将浇注的生坯从铸模中除去。
粉浆然后可在80-110℃的温度下喷雾干燥,以产生颗粒状ITO粉末,将其在80-110Mpa的压力下经历冷等静压,以产生压实的生坯。
然后将得到的生坯在40-80℃温度范围的烘箱中干燥3-5天,然后在氧气中以1000℃-1750℃温度在加热炉中烧制。靶的形状和大小不受限制,可以通过改变铸模的形状和大小来简便地改变,可以使用>100cm2尺寸的铸模。能够获得理想的尺寸和大小的靶而不会受到任何破裂和弯曲。
根据本发明的过程,可以制备相对密度≥99%的ITO靶。
实施例
实施例1
将氧化铟(III)和氧化锡(IV)从它们的硝酸盐化合物的溶液中共沉淀。用去离子水进行沉淀物的洗涤。将沉淀的氢氧化物过滤,然后在800℃-1200℃下煅烧,以产生具有表面积在1-5m2/g范围的氧化物粉末。用10%糖类分散体轻轻喷射尺寸为1000mm×700mm并且空腔厚度为20mm的熟石膏铸模。将含有96000g表面积为3.5m2/g的和组合物氧化铟(III)90%重量百分比的纯度为99.999%的ITO粉末、1800g22%重量百分比的聚羧酸分散剂如Daravan C的溶液,500g浓度为55%重量百分比的丙烯酸类乳液粘结剂、140g氧化物如MxOy(其中,M=砷、锑、铋,X=2,Y=3;M=硒、碲,X=1,Y=2)和10000g去离子水的浆液置入50000升容积的高密度聚丙烯罐中,使用具有直径为12mm的氧化钇稳定化的氧化锆珠的旋转球磨机将整个混合物完全混合72小时,以得到用于粉浆浇注ITO生坯的表面积为9m2/g的紧密共混的ITO粉末的粉浆。
使用超声搅拌将得到的粉浆充分除气,然后在30psi的压力下注入多孔熟石膏铸模中。将该压力保持4小时。此期间之后,除去压力,打开铸模。取出ITO生坯,在25℃下干燥7天,然后在50℃下干燥7天。将其在1700℃下在氧气中烧制10小时。将烧制的高密度ITO靶精密地切割,表面抛光,在高纯度异丙醇中清洗并空气干燥,得到准备粘结到铜背板并用于溅射工艺的商业加工靶。所有上述操作在10000级无尘室中进行。
所得到的靶具有99.5%的相对密度。
实施例2
将氧化铟(III)和氧化锡(IV)从它们的硝酸盐化合物的溶液中共沉淀。用去离子水进行沉淀物的洗涤。将沉淀的氢氧化物过滤,然后在800℃-1200℃下煅烧,以产生具有表面积在1-5m2/g范围的氧化物粉末。将含有96000g表面积为3.5m2/g和组合物氧化铟(III)90%重量百分比的,纯度为99.999%的ITO粉末、1800g22%重量百分比的聚羧酸分散剂如Daravan C的溶液、500g浓度为55%重量百分比的丙烯酸类乳液粘结剂、140g氧化物如MxOy(其中,M=砷、锑、铋,X=2,Y=3;M=硒、碲,X=1,Y=2)和10000g去离子水的浆液置入50000升容积的高密度聚丙烯罐中,使用具有直径为12mm的氧化钇稳定化的氧化锆珠的旋转球磨机将整个混合物完全混合72小时,以得到表面积为9m2/g的紧密共混的ITO粉末的粉浆。将粉浆注入固定在加压粉浆浇注机中的尺寸为1500mm×800mm×20mm的多孔聚合物铸模中,并在10MPa压力下浇注10-30分钟。随后将铸模打开,将浇注的生坯从铸模中除去。
将ITO生坯在25℃下干燥7天,然后在50℃下干燥7天。随后将其在1700℃下在氧气中烧制10小时。将烧制的高密度ITO靶精密地切割,表面抛光,在高纯度异丙醇中清洗并空气干燥,得到准备粘结到铜背板并用于溅射工艺的商业加工靶。所有上述操作在10000级无尘室中进行。
所得到的靶具有99.8%的相对密度。
实施例3
将氧化铟(III)和氧化锡(IV)从它们的硝酸盐化合物的溶液中共沉淀。用去离子水进行沉淀物的洗涤。将沉淀的氢氧化物过滤,然后在800℃-1200℃下煅烧,以产生具有在1-5m2/g范围的表面积的氧化物粉末。将含有96000g表面积为3.5m2/g和组合物氧化铟(III)90%重量百分比的,纯度为99.999%的ITO粉末、1800g22%重量百分比的聚羧酸分散剂如Daravan C的溶液、500g浓度为55%重量百分比的丙烯酸类乳液粘结剂、140g氧化物如MxOy(其中,M=砷、锑、铋,X=2,Y=3;M=硒、碲,X=1,Y=2)和10000g去离子水的浆液置入50000升容积的高密度聚丙烯罐中,使用具有直径为12mm的氧化钇稳定化的氧化锆珠的旋转球磨机将整个混合物完全混合72小时,以得到表面积为8.5m2/g的紧密共混的ITO粉末的粉浆。通过使用在110℃下操作的喷雾干燥,将粉浆喷雾干燥,以产生颗粒状ITO粉末,随后使用在120MPa压力的冷等静压,在直径为1500mm的不锈钢铸模中压实,以产生压实的ITO生坯。
将ITO生坯在25℃下干燥7天,然后在50℃下干燥7天。随后将其在1700℃下在氧气中烧制10小时。将烧制的高密度ITO靶精密地切割,表面抛光,在高纯度异丙醇中清洗并空气干燥,得到准备粘结到铜背板并用于溅射工艺的商业加工靶。所有上述操作在10000级无尘室中进行。
所得到的靶具有99.9%的相对密度。
实施例4
除了向浆液中添加140g砷化铟外,使用与实施例1、2和3相同的方法。所得到的靶具有99.2%的相对密度。
实施例5
除了向浆液中添加140g锑化铟外,使用与实施例1、2和3相同的方法。所得到的靶具有99.9%的密度。
实施例6
除了向浆液中添加140g硒化铟外,使用与实施例1、2和3相同的方法。所得到的靶具有99.7%的密度。
实施例7
除了向浆液中添加140g碲化铟外,使用与实施例1、2和3相同的方法。所得到的靶具有99.9%的密度。
实施例7
除了向浆液中添加140g硼酸外,使用与实施例1、2和3相同的方法。所得到的靶具有99.7%的密度。
实施例8
除了向浆液中添加140g磷酸铋(III)外,使用与实施例1、2和3相同的方法。所得到的靶具有99.9%的密度。
实施例9
除了向浆液中添加140g水合磷酸硼(III)外,使用与实施例1、2和3相同的方法。所得到的靶具有99.4%的密度。
实施例10
除了向浆液中添加140g氧化砷(III)外,使用与实施例1、2和3相同的方法。所得到的靶具有99.9%的密度。
实施例11
除了向浆液中添加140g氧化锑(III)外,使用与实施例1、2和3相同的方法。所得到的靶具有99.8%的密度。
实施例12
除了向浆液中添加140g氧化铋(III)外,使用与实施例1、2和3相同的方法。所得到的靶具有99.9%的密度。
因此,能够改进在溅射过程期间ITO靶的应用效率。
此外,本发明提供了一种方法,通过该方法能够制备任意形状的大ITO靶,而不使用如氯化氢或氯气对生物有机体均高度有毒的危险材料。
另外,能够制备在整个靶体上具有优异的密度均匀性、化学计量、导电性和导热性,甚至大于250cm2的靶尺寸而且相对密度大于理论的99%的ITO靶。
Claims (18)
1.一种生产高密度ITO靶的方法,所述方法包括形成ITO粉末含量大于80%重量百分比的ITO粉末的含水粉浆,所述粉浆包含一种或多种砷、锑、铋、硒、碲和/或硼的化合物形式的烧结助剂。
2.根据权利要求1所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的氧化砷(III)。
3.根据权利要求1或2所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的氧化锑(III)。
4.根据权利要求1、2或3所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的氧化铋(III)。
5.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的硼酸。
6.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的氧化碲(IV)。
7.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为ITO粉末的0.001%-1%重量百分比的氧化铋(III)。
8.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的砷化铟(III)。
9.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的锑化铟(III)。
10.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的硒化铟(III)。
11.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的碲化铟(III)。
12.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的磷酸铋(III)。
13.根据前述权利要求中任意一项所述的方法,其中,烧结助剂中的一种为浓度为干燥ITO粉末的0.001%-1%重量百分比的磷酸硼(III)。
14.根据前述权利要求中任意一项所述的方法,所述方法还包括使用多孔熟石膏铸模浇注粉浆,以生产ITO生坯。
15.根据权利要求1-13中任意一项所述的方法,所述方法还包括使用固定在加压粉浆浇注机中的多孔聚合物铸模浇注粉浆,以产生ITO生坯。
16.根据权利要求1-13中任意一项所述的方法,所述方法还包括喷雾干燥粉浆,以生产颗粒状ITO粉末,使用冷等静压将其压实成为生坯。
17.根据权利要求14、15或16所述的方法,所述方法还包括在高达1700℃的峰值温度的加热炉中烧制生坯。
18.一种ITO靶,所述ITO靶使用前述权利要求中任意一项所述的方法制造。
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GB1013255.3A GB2482544A (en) | 2010-08-06 | 2010-08-06 | Making high density indium tin oxide sputtering targets |
PCT/IB2011/001818 WO2012017305A1 (en) | 2010-08-06 | 2011-08-05 | Manufacture of high density indium tin oxide (ito) sputtering target |
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EP (1) | EP2601328A4 (zh) |
JP (1) | JP2013533391A (zh) |
KR (1) | KR20130099032A (zh) |
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GB (1) | GB2482544A (zh) |
WO (1) | WO2012017305A1 (zh) |
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CN104591740A (zh) * | 2015-01-12 | 2015-05-06 | 吴江佳亿电子科技有限公司 | 一种耐冲击陶瓷材料及其制备方法 |
CN108947520A (zh) * | 2018-06-26 | 2018-12-07 | 株洲冶炼集团股份有限公司 | 一种ito烧结靶材的制备方法 |
CN111943650A (zh) * | 2020-07-22 | 2020-11-17 | 长沙壹纳光电材料有限公司 | 一种用于活化等离子沉积技术的iwo靶材及其制备方法 |
CN113458398A (zh) * | 2021-06-09 | 2021-10-01 | 北京科技大学 | 一种注射浆料实现金属注射成形的方法 |
CN115159975A (zh) * | 2022-07-04 | 2022-10-11 | 中山智隆新材料科技有限公司 | 一种ito溅射靶材的制备方法 |
WO2022247386A1 (zh) * | 2021-05-28 | 2022-12-01 | 通威太阳能(合肥)有限公司 | 一种烧结体、靶材及其制备方法 |
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JP5869361B2 (ja) * | 2012-02-14 | 2016-02-24 | 株式会社アルバック | Ito粉末の製造方法及びitoスパッタリングターゲットの製造方法 |
CN104603320B (zh) * | 2012-08-31 | 2017-04-05 | 株式会社钟化 | 带透明电极的基板的制造方法、以及带透明电极的基板 |
KR20160073685A (ko) | 2014-12-17 | 2016-06-27 | 희성금속 주식회사 | 고강도를 가지는 스퍼터링용 산화물 타겟의 제조방법 |
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CN104591740A (zh) * | 2015-01-12 | 2015-05-06 | 吴江佳亿电子科技有限公司 | 一种耐冲击陶瓷材料及其制备方法 |
CN108947520A (zh) * | 2018-06-26 | 2018-12-07 | 株洲冶炼集团股份有限公司 | 一种ito烧结靶材的制备方法 |
CN108947520B (zh) * | 2018-06-26 | 2021-06-11 | 株洲冶炼集团股份有限公司 | 一种ito烧结靶材的制备方法 |
CN111943650A (zh) * | 2020-07-22 | 2020-11-17 | 长沙壹纳光电材料有限公司 | 一种用于活化等离子沉积技术的iwo靶材及其制备方法 |
WO2022247386A1 (zh) * | 2021-05-28 | 2022-12-01 | 通威太阳能(合肥)有限公司 | 一种烧结体、靶材及其制备方法 |
CN113458398A (zh) * | 2021-06-09 | 2021-10-01 | 北京科技大学 | 一种注射浆料实现金属注射成形的方法 |
CN115159975A (zh) * | 2022-07-04 | 2022-10-11 | 中山智隆新材料科技有限公司 | 一种ito溅射靶材的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
EP2601328A1 (en) | 2013-06-12 |
GB2482544A (en) | 2012-02-08 |
KR20130099032A (ko) | 2013-09-05 |
US20130206590A1 (en) | 2013-08-15 |
JP2013533391A (ja) | 2013-08-22 |
GB201013255D0 (en) | 2010-09-22 |
WO2012017305A1 (en) | 2012-02-09 |
EP2601328A4 (en) | 2014-02-05 |
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