CN102089258B - 氧化镧基烧结体、包含该烧结体的溅射靶、氧化镧基烧结体的制造方法及通过该制造方法制造溅射靶的方法 - Google Patents
氧化镧基烧结体、包含该烧结体的溅射靶、氧化镧基烧结体的制造方法及通过该制造方法制造溅射靶的方法 Download PDFInfo
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- CN102089258B CN102089258B CN200980126610.3A CN200980126610A CN102089258B CN 102089258 B CN102089258 B CN 102089258B CN 200980126610 A CN200980126610 A CN 200980126610A CN 102089258 B CN102089258 B CN 102089258B
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- lanthanum
- lanthanum oxide
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005477 sputtering target Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 230000008569 process Effects 0.000 title abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 239000001257 hydrogen Substances 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 42
- 229910052719 titanium Inorganic materials 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 29
- 229910052735 hafnium Inorganic materials 0.000 claims description 29
- 229910052726 zirconium Inorganic materials 0.000 claims description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 19
- 239000004615 ingredient Substances 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 14
- 241000588731 Hafnia Species 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229920002994 synthetic fiber Polymers 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 229910017569 La2(CO3)3 Inorganic materials 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 229910000449 hafnium oxide Inorganic materials 0.000 abstract 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 78
- 238000009461 vacuum packaging Methods 0.000 description 33
- 230000000694 effects Effects 0.000 description 31
- 238000012360 testing method Methods 0.000 description 25
- 229910052746 lanthanum Inorganic materials 0.000 description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 19
- 230000005764 inhibitory process Effects 0.000 description 12
- 229910052747 lanthanoid Inorganic materials 0.000 description 9
- 150000002602 lanthanoids Chemical class 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 7
- 229910052761 rare earth metal Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910004143 HfON Inorganic materials 0.000 description 3
- -1 and in addition Chemical compound 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 150000004678 hydrides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910004140 HfO Inorganic materials 0.000 description 2
- 229910004129 HfSiO Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 235000020061 kirsch Nutrition 0.000 description 1
- 150000002604 lanthanum compounds Chemical class 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910000048 titanium hydride Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C04B35/46—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 titanium oxides or titanates
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- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/486—Fine ceramics
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
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Abstract
本发明涉及一种氧化镧基烧结体,以氧化镧作为基础成分,含有氧化钛、氧化锆、氧化铪的一种或两种以上,其余为氧化镧和不可避免的杂质。还涉及一种氧化镧基烧结体的制造方法,使用La2(CO3)3粉末或La2O3粉末作为氧化镧原料粉末,使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物,将其以用金属换算添加氧化物的金属成分的组成比为规定值的方式进行配合并混合后,将该混合粉末在大气中进行加热合成,然后将该合成材料粉碎得到粉末,然后将该合成粉末进行热压得到烧结体。本发明可以防止与水分或二氧化碳结合形成氢氧化物等而变为粉末状,可以长期保存。另外,本发明提供通过使用该溅射靶进行成膜,可以高效且稳定地提供High-K栅绝缘膜用氧化物的技术。
Description
技术领域
本发明涉及以氧化镧(La)为基础成分,包含由钛(Ti)、锆(Zr)、铪(Hf)的一种或两种以上组成的添加氧化物的氧化镧基烧结体、包含该烧结体的溅射靶、氧化镧基烧结体的制造方法及通过该制造方法制造溅射靶的方法。
背景技术
最近,作为下一代MOSFET中的栅绝缘膜,要求薄膜化,但是,迄今作为栅绝缘膜使用的SiO2,通过隧道效应造成漏电流增加,难以正常工作。
因此,作为代替SiO2的材料,提出了具有高介电常数、高热稳定性、对硅中的空穴和电子具有高能障的HfO2、ZrO2、Al2O3、La2O3等所谓的High-K材料。
这些材料中有前景的是以HfO2为基础的材料体系,发布了作为下一代MOSFET中的栅绝缘膜。最近有报道称,通过将HfO系或者HfON系的High-K材料与氧化镧(La2O3)组合使用可以得到降低阈值电压等特性改善(参考非专利文献1)。另外公开了特别使用La2Hf2O7作为LaHfO系的材料来控制金属栅電极的有效功函数(参考专利文献1参照)。
从而镧成为引起关注的材料。
镧(La)是包括在稀土元素中的元素,作为矿物资源以混合复合氧化物形式包含在地壳中。稀土元素是从比较稀少地存在的矿物中分离出来的,因此具有这样的名称,但是从地壳整体来看绝对不稀少。
镧为原子序数57、原子量138.9的白色金属,在常温下具有双六方最密堆积结构(複六方最密構造)。熔点921℃、沸点3500℃、密度6.15g/cm3,在大气中表面被氧化,逐渐溶于水中。可溶于热水、酸。无延性,但稍有展性。电阻率为5.70×10-6Ω·cm。在445℃以上燃烧形成氧化物(La2O3)(参考理化学辞典)。
稀土元素一般以氧化数为3的化合物稳定,镧也是3价。
金属镧存在纯化时容易氧化的问题,因此是难以高纯度化的材料,从而不存在高纯度制品。另外,金属镧在大气中放置的情况下,短时间内氧化变为黑色,因此存在不容易操作的问题。
因此,对于镧(氧化镧)而言,可以说尚处于研究阶段,在对这样的镧(氧化镧)的特性进行调查的情况下,如果金属镧自身作为溅射靶材而存在,则可以在衬底上形成镧的薄膜,并且容易对与硅衬底的界面行为、以及通过进一步形成镧化合物而对高介电常数栅绝缘膜等的特性进行调查,另外,还具有作为制品的自由度增大的巨大优点。
但是,即使制作镧溅射靶,如上所述,其在大气中短时间内(约10分钟)发生氧化。在靶上形成氧化膜时,电导率下降,导致溅射不良。另外,在大气中长时间放置时,与大气中的水分反应而成为由白色的氢氧化物粉末覆盖的状态,造成不能正常溅射的问题。
因此,在靶制作后,需要立即进行真空包装或者用油脂包覆的抗氧化对策,但随时进行真空包装是非常繁杂的作业。同样地,用油脂包覆的事实对于要求清洁度的溅射靶而言,由于伴随油脂的除去作业,因此同样伴随繁杂的作业。
鉴于以上问题,镧元素的靶材迄今未实际应用。如上所述,不能制造耐受实际应用的氧化镧靶。
另一方面,为了制作氧化镧膜,使用氧化镧靶的方法与将金属镧与氧进行反应性溅射的方法或者在形成金属镧膜后进行氧化的方法相比,工序简单,可以形成氧量均匀的膜。但是,氧化镧与大气中的水分的反应比金属镧发生得快,在非常的短的时间内成为粉末状,最后完全破坏。因此,在通过工业上通常使用的PVD法、特别是溅射法制作La2O3膜的情况下,非常难以提供能够耐受实际应用的溅射靶。
非专利文献1:ALSHAREEF H.N.,QUEVEDO-LOPEZ M.,WEN H.C.,HARRIS R.,KIRSCH P.,MAJHI P.,LEE B.H.,JAMMY R.,著「WOrkfunctiOn engineering using lanthanum Oxide interfacial layers」Appl.Phys.Lett.,第89卷,第23期,232103-232103-3页,(2006)
专利文献1:日本特开2007-324593号公报
发明内容
如上述的现有技术所述,金属镧容易与氧结合,另外,氧化镧与水分和二氧化碳结合形成氢氧化物等而变为粉末状,因此,难以长时间保存,难以以溅射靶的形式产品化。
本发明的课题在于,提供以氧化镧(La)为基础成分、包含由钛(Ti)、锆(Zr)、铪(Hf)的一种或两种以上组成的添加氧化物的氧化镧基烧结体、包含该烧结体的溅射靶、氧化镧基烧结体的制造方法以及通过该制造方法制造溅射靶的方法,由此,防止与水分或二氧化碳结合形成氢氧化物等而变为粉末状,可以长期保存。另外,本发明的课题在于提供通过使用该溅射靶进行成膜,可以高效且稳定地提供High-K栅绝缘膜用氧化物的技术。
如上述发明想要解决的课题所述,金属镧容易与氧结合,另外,氧化镧与水分结合形成氢氧化物,从而均难以长期保存。本申请发明以氧化镧为基础成分,在其中添加氧化钛、氧化锆、氧化铪的一种或两种以上,以烧结体或溅射靶的形式使用。另外,这些烧结体及靶的成分组成包含新物质。
根据以上内容,本申请发明提供:
1)一种氧化镧基烧结体,以氧化镧作为基础成分,其特征在于,含有氧化钛、氧化锆、氧化铪的一种或两种以上,其余为氧化镧和不可避免的杂质;
2)如上述1)所述的氧化镧基烧结体,其特征在于,相对于烧结体中的金属元素的合计成分量,钛、锆、铪的金属元素的量为1摩尔%以上且低于50摩尔%;
3)如上述1)所述的氧化镧基烧结体,其特征在于,相对于烧结体中的金属元素的合计成分量,钛、锆、铪的金属元素的量为10摩尔%以上且低于50摩尔%;
4)如上述1)至3)中任一项所述的氧化镧基烧结体,其特征在于,氢和碳各自为25重量ppm以下,相对密度为96%以上,最大粒径为50μm以下,平均粒径为5μm以上;
5)一种溅射靶,包含上述1)~4)中任一项所述的烧结体。
另外,本申请发明提供:
6)一种氧化镧基烧结体的制造方法,其特征在于,使用La2(CO3)3粉末或La2O3粉末作为氧化镧原料粉末,使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物,将其以添加氧化物的金属成分相对于La的组成比为规定值的方式进行配合并混合后,将该混合粉末在大气中进行加热合成,然后将该合成材料粉碎得到粉末,然后将该合成粉末进行热压得到烧结体;
7)如上述1)~5)中任一项所述的氧化镧基烧结体的制造方法,其特征在于,使用La2(CO3)3粉末或La2O3粉末作为氧化镧原料粉末,使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物,将其以添加氧化物的金属成分相对于La的组成比为规定值的方式进行配合并混合后,将该混合粉末在大气中进行加热合成,然后将该合成材料粉碎得到粉末,然后将该合成粉末进行热压得到烧结体;
8)如上述6)或7)所述的氧化镧基烧结体的制造方法,其特征在于,混合通过湿式球磨机进行,合成在大气中、在1350℃~1550℃下加热5小时~25小时来制造;
9)如上述6)~8)中任一项所述的氧化镧基烧结体的制造方法,其特征在于,热压在1200℃~1500℃下、真空中进行1小时~5小时;
10)通过上述6)~8)中任一项所述的氧化镧基烧结体的制造方法制造溅射靶的方法。
发明效果
将氧化镧烧结体溅射靶在大气中长时间放置时,由于潮解性而与水分反应,成为由氢氧化物的白色粉末覆盖的状态,产生不能正常溅射的问题。另外,吸收大气中的二氧化碳而崩解为碳酸镧的粉末。本发明的靶,可以延迟这些问题的发生,可以保存到实际应用上没有问题的期限。
作为添加氧化物的氧化钛、氧化锆、氧化铪作为High-k材料均是有效的,但是认为,特别是添加作为HfO系或HfON系、HfSiO系或HfSiON系(High-k材料)使用的Hf氧化物的情况,比起含有氧化钛、氧化锆的情况,与钛、锆向High-k材料的扩散相伴随的漏电流增加的问题少,更加有效。
具体实施方式
本发明的氧化物烧结体溅射靶,是以氧化镧作为基础成分的烧结体及使用该烧结体的溅射靶,所述烧结体的特征在于,含有氧化钛、氧化锆、氧化铪的一种或两种以上,其余为氧化镧和不可避免的杂质。
该烧结体和靶与镧或氧化镧相比,具有可以极大抑制下列现象的显著效果:由于潮解性而与水分反应,从而由氢氧化物的白色粉末覆盖而崩解的现象:或者吸收大气中的二氧化碳而崩解为碳酸镧的粉末的现象。这是本申请发明的中心技术构思。本申请人调查的现有技术中,作为烧结体或靶,不存在具有这种组成的烧结体和靶。
上述镧或氧化镧的崩解抑制理论,不一定清楚,但是,通过添加作为添加成分的氧化钛、氧化锆、氧化铪提供大的贡献这一点,却是从许多实验中可以明确看出的。对此,通过后述的实施例和比较例详细进行说明。
氧化钛、氧化锆、氧化铪的添加,由于不是单独地使用镧或氧化镧,因此在材料的使用上有限制。但是,由于这些材料是均可以有效地用作High-K栅绝缘膜用氧化物的材料,因此,添加本身不会产生负面效果。
其添加量可以根据使用目的和用途进行选择。这些材料中,作为High-K栅绝缘膜用氧化物,特别是氧化铪的添加是有效的。这是因为:在使用氧化钛、氧化锆的情况下,微量的钛或锆向High-k材料扩散,从而产生漏电流稍稍增加的问题。氧化铪不产生该问题。
对镧(La)和钛(Ti)、锆(Zr)、铪(Hf)的氧化物的添加进行考虑时,相对于氧化物中的La和添加氧化物的金属成分(钛、锆、铪的合计)的合计量,所述添加氧化物的金属成分(钛、锆、铪的合计)、即(Ti、Zr、Hf)/(La+Ti、Zr、Hf)为1摩尔%以上且低于50摩尔%是良好的。为了更有效地防止崩解,优选10摩尔%以上。
低于1摩尔%时,防止因氧化镧的潮解性引起的崩解的效果小,为50摩尔%以上时,虽然对于防止崩解的效果有效,但是作为氧化镧的特性的利用效果小。这是因为例如,在Hf更多的情况下,高介电常数氧化物(例如,La2Hf2O7、La2Zr2O7)的特性具有优势地位,从而特性产生差异。
本申请发明的前提是作为High-K材料的应用,通过组合使用氧化镧(La2O3),可以得到降低阈值电压等特性。
另外,作为附加要件,降低烧结体的氢含量和碳含量、提高密度、形成最佳结晶粒径,对于进一步提高本申请发明的烧结体和靶的特性都是有效的。为了该目的,本申请发明提供氢和碳各自为25重量ppm以下、相对密度为96%以上、最大粒径为50μm以下、平均粒径为5μm以上且20μm以下的氧化镧基烧结体和靶。
烧结体和靶中存在氢和碳,由于是引起与气氛中的水分或二氧化碳的反应的基点,因此减少其含量是有效的。另外,提高密度对于减少与上述气氛的接触面积是必要的。密度更优选设为98%。由此,可以减少烧结体中的贯通孔,防止从内部开始的崩解。
另外,可以使烧结体的结晶粒径较大,减少晶粒间界,减少从晶粒间界开始的崩解。由此,如果增大结晶粒径,则晶粒间界面积减小,因此可以有效地减少从晶粒间界开始的崩解,但是,由于过度地增大结晶粒径时难以提高密度,因此可以说,为了提高密度,最大粒径优选为50μm以下。
但是,这些不过是附加的优选要件,没有必要限于这些条件。
制造该氧化物烧结体靶时,使用La2(CO3)3粉末或La2O3粉末作为原料粉末,并且使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物。以相对于金属La与添加氧化物中的金属成分钛、锆、铪的总合计量,添加氧化物中的金属成分钛、锆、铪的合计量为1摩尔%以上且低于50摩尔%的方式进行配合。该配合比特别优选为10摩尔%以上且低于50摩尔%。
但是,如果通过热処理等能够产生氧化物,则不限于上述的氧化物。例如,作为这样的原料,关于La,有氢氧化镧、硝酸镧、氯化镧等。另外,如果能够充分地控制,也可以使用金属镧。
关于Ti、Zr,Hf,如果能够充分控制,也可以使用金属粉末或粉碎性好的氢化粉末。将其混合后,在氧化性气氛中进行加热合成,然后将该合成材料粉碎得到粉末,再将该合成粉末进行热压得到烧结体,可以由此来进行制造。
在以氢化粉末(氢化钛、氢化锆、氢化铪)为原料的情况下,需要在真空气氛中或者惰性气氛中进行充分的脱氢処理。
混合通过湿式球磨机进行,合成在大气中、在1350℃~1550℃下加热约5小时~约25小时来进行是推荐的制造条件。
另外,热压在1200℃~1500℃下、真空中、进行1小时~5小时的烧结条件,同样是推荐的制造条件。以上是有效进行合成和烧结的条件。因此,应该理解,当然可以设定为除此以外的条件以及附加其它条件。
由此,可以得到相对密度为96%以上、更优选98%以上、最大粒径为50μm以下、更优选平均粒径为5μm以上且20μm以下的氧化物烧结体溅射靶。当然提高密度和细化结晶粒径是可以抑制结瘤或粉粒的产生、可以进行均匀成膜的优选条件。
一般而言,镧中含有的稀土元素,除镧(La)以外,还有Sc、Y、Ce、Pr、Nd、Pm、Sm、Eu、Gd、D、Tb、Dy、Ho、Er、Tm、Yb、Lu,由于特性近似,因此难以从La中分离纯化。特别是Ce与La近似,因此不容易减少Ce。
但是,可以理解,这些稀土元素由于性质近似,因此,如果以稀土元素合计低于1000重量ppm,则不会别地成问题。因此,本申请发明中镧的使用中,含有该水平的稀土元素作为不可避免的杂质是允许的。
此外,还存在不可避免地混入的杂质。例如,Ti、Zr、Hf的化学特性相近,因此Zr和Hf难以分离。Hf中含有微量的Zr。另外,Zr中也含有微量的Hf,但是,这些均不会成为大的问题。但是,为了明确地有效利用添加Hf(氧化铪)的特性,认为当然优选减少不可避免地混入的Zr。这是因为,如上所述,Zr有可能会扩散到作为High-k(高介电常数)材料的以Hf为基础的HfO、HfON,HfSiO和HfSiON中,从而改变介电常数。
但是,本申请发明的目的在于抑制氧化镧的崩解从而得到实际应用的溅射靶,因此,包含这些不可避免的杂质。另外,纯度方面,除上述特殊的不可避免的杂质外,优选除气体成分以外的纯度为3N以上。
一般而言,作为气体成分,存在C、N、O、S、H。在为氧化镧的情况下,减少C、H是重要的。C、H各自不仅会促进与保存气氛中的二氧化碳、水分的反应,而且自身含有的氧与气氛中的氧反应形成碳酸镧、氢氧化镧,从而崩解为粉末状,因此减少其含量是重要的。因此,比起在氧(大气)气氛中的烧结,更优选通过在真空中、惰性气体中的热压进行烧结。
实施例
以下,对实施例进行说明。另外,该实施例仅仅用于容易理解本发明,不限制本发明。即,本发明的技术构思范围内的其它实施例和变形,也包含在本发明中。另外,下述内容中,作为参考例举出的例子,虽然从本申请的目的来看不充分,但是仍然观察到与本申请发明近似的特性改善。关于比较例1,在第22页22~26行中记载。
(参考例1-3、实施例1-25)
使用La2(CO3)3粉末和HfO2、ZrO2、TiO2粉末作为原料粉末,以相对于包含La的金属成分的合计量,Hf、Zr、Ti的量为0.5摩尔%~49摩尔%的方式,将原料粉末进行配合,并使用湿式球磨机进行混合。将该混合粉末在大气中在1450℃下加热20小时进行合成。
另外,在使用La2O3粉末作为La氧化物的情况下,也得到同样结果,因此,本实施例对使用La2(CO3)3粉末的情况进行说明。
将其进行机械加工得到评价用的烧结体。烧结体为它们的复合氧化物。在大气中、或者恒温恒湿槽(温度40℃、湿度90%)中调查评价用烧结体的稳定性。通过XRD确认粉末化的物质主要是镧的氢氧化物(La(OH)3)。
实施例所示的烧结体,作为靶与背衬板焊接,并根据需要进行真空密封(或者在惰性气体气氛中),从而可以用于实际的半导体制造工艺。
另外,上述原料粉末的混合条件、合成条件、热压条件均为代表性的条件。第4页21行至第5页第10行中记载的适当条件可以任意选择。
(参考例1)
参考例1的复合氧化物烧结体,以复合氧化物烧结体(氧化镧和氧化铪)的金属换算,含有铪0.5摩尔%,即以Hf/(La+Hf)的摩尔%计,含有Hf为0.5%。以下,其他的参考例和实施例也同样。另外,仅供参考,以Hf/(La+Hf)的摩尔%计,含有Hf为50摩尔%为La2Hf2O7的组成,La2O3为33.3摩尔%、HfO2为66.7摩尔%。
碳含量为35ppm、氢29ppm、相对密度为95%、最大粒径为41μm、平均粒径为12μm。此时,HfO2量比本申请发明的优选条件稍少,碳含量比本申请发明的优选条件稍多,相对密度低一些,为95%。结果,在大气中经过3周,烧结体崩解为粉末状。
但是,在真空包装中,4个月间,未观察到表面的粉末化。该水平的烧结体,崩解的进行速度稍大,但是,如果使用真空包装,则可以说处于实际应用水平的范围。评价为△。
(参考例2)
参考例2的复合氧化物烧结体,以金属换算,ZrO2按Zr换算含有0.5摩尔%。碳含量为23ppm、氢19ppm、相对密度为97%、最大粒径为37μm、平均粒径为9μm。此时,ZrO2量比本申请发明的优选条件稍少,但是相对密度稍高,为97%。结果,在大气中经过4周,烧结体崩解为粉末状。比参考例1有一些改善。
但是,在真空包装中,4个月间,未观察到表面的粉末化。该水平的烧结体,崩解的进行速度稍大,但是,如果使用真空包装,则可以说处于实际应用水平的范围。评价为△。
(参考例3)
参考例3的复合氧化物烧结体,以金属换算,TiO2按Ti换算含有0.5摩尔%。碳含量为46ppm、氢50ppm、相对密度为95%、最大粒径为53μm、平均粒径为11μm。此时,TiO2量比本申请发明的优选条件稍少,碳含量和氢量比本申请发明优选条件稍多,最大粒径稍大,为53μm,相对密度低一些,为95%。结果,在大气中经过3周,烧结体崩解为粉末状。
但是,在真空包装中,至4个月间,未观察到表面的粉末化。该水平的烧结体,崩解的进行速度稍大,但是,如果使用真空包装,则可以说处于实际应用水平的范围。评价为△。
(实施例1)
实施例1的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有1摩尔%。碳含量为37ppm、氢30ppm、相对密度为95%、最大粒径为40μm、平均粒径为10μm。此时,HfO2量符合本申请发明的优选条件。碳含量、氢含量比本申请发明的优选条件稍多,相对密度低一些,为95%。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中第4周,烧结体崩解为粉末状。而且,在真空包装中经6个月,6个月间未观察到表面的粉末化。可以确认,该HfO2的存在具有大的抑制烧结体崩解的效果。为实际应用水平,评价为○。
(实施例2)
实施例2的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有1摩尔%。碳含量为15ppm、氢20ppm、相对密度为97%、最大粒径为42μm、平均粒径为15μm。此时,各条件均符合本申请发明的优选条件。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中第4周,仅烧结体的表面崩解为粉末状。而且,在真空包装中,10个月间未观察到表面的粉末化。可以确认,该HfO2的存在以及附加条件的优化具有大的抑制烧结体崩解的效果。为实际应用水平,评价为○。
(实施例3)
实施例3的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有5摩尔%。碳含量为53ppm、氢47ppm、相对密度为97%、最大粒径为41μm、平均粒径为5μm。此时,碳和氢的含量多,其它条件符合本申请发明的优选条件。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中第4周,烧结体崩解为粉末状。而且,在真空包装中,6个月间未观察到表面的粉末化。可以确认,该复合氧化物烧结体中存在过量的碳和氢,成为稍稍崩解的促进因素。但是,该实施例3的复合氧化物烧结体,整体上可以确认具有大的抑制烧结体崩解的效果。为实际应用水平,评价为○。
(实施例4)
实施例4的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有5摩尔%。碳含量为26ppm、氢28ppm、相对密度为98%、最大粒径为36μm、平均粒径为13μm。此时,该复合氧化物烧结体中碳和氢稍稍过量存在。但是,其量比实施例6少。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中第4周,仅烧结体表面崩解为粉末状。而且,在真空包装中,10个月间未观察到表面的粉末化。
可以确认,该复合氧化物烧结体中存在稍微过量的碳和氢,成为稍稍崩解的促进因素。但是,可以确认该实施例4的复合氧化物烧结体的抑制崩解的效果超过实施例6。为实际应用水平,评价为○。
(实施例5)
实施例5的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有10摩尔%。碳含量为76ppm、氢28ppm、相对密度为95%、最大粒径为63μm、平均粒径为3μm。此时,该复合氧化物烧结体中存在过量的碳和氢,最大粒径、平均粒径这样的附加要件不处于最佳范围。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。但是,测定表面硬度发现有降低一些的倾向。
而且,在真空包装中经过一年,逐渐观察到表面的粉末化。可以确认,该复合氧化物烧结体中Hf的存在量大,即使其它附加因素在本申请发明的条件以外,也具有大的抑制崩解的效果。评价为◎。
(实施例6)
实施例6的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有10摩尔%。碳含量为18ppm、氢20ppm、相对密度为96%、最大粒径为23μm、平均粒径为15μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过1年也未观察到表面的粉末化。可以确认,在Hf的存在以及其它附加因素符合本申请发明条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例7)
实施例7的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有35摩尔%。碳含量为73ppm、氢52ppm、相对密度为98%、最大粒径为37μm、平均粒径为8μm。此时,该复合氧化物烧结体中相当过量地存在碳和氢。其它附加要件符合最佳范围。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。但是,测定表面硬度发现有降低一些的倾向。
而且,在真空包装中,经过一年,逐渐观察到表面的粉末化。但是,测定表面的硬度发现有降低一些的倾向。
可以确认,在Hf的存在以及其它附加因素符合本申请发明条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例8)
实施例8的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有35摩尔%。碳含量为13ppm、氢21ppm、相对密度为98%、最大粒径为30μm、平均粒径为13μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年也未观察到粉末化。可以确认,在Hf的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例9)
实施例9的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有45摩尔%。碳含量为73ppm、氢52ppm、相对密度为98%、最大粒径为37μm、平均粒径为8μm。此时,该复合氧化物烧结体中相当过量地存在碳和氢,其它附加要件处于最佳范围。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。但是,测定表面硬度发现有降低一些的倾向。
而且,在真空包装中,经过一年,逐渐观察到表面的粉末化。可以确认,在Hf的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例10)
实施例10的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有45摩尔%。碳含量为10ppm、氢25ppm、相对密度为98%、最大粒径为31μm、平均粒径为14μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年也未观察到粉末化。可以确认,在Hf的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例11)
实施例11的复合氧化物烧结体,以金属换算,HfO2按Hf换算含有48摩尔%。碳含量为23ppm、氢24ppm、相对密度为97%、最大粒径为18μm、平均粒径为10μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年也未观察到粉末化。可以确认,在Hf的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例12)
实施例12的复合氧化物烧结体,以金属换算,ZrO2按Zr换算含有5摩尔%。碳含量为20ppm、氢14ppm、相对密度为98%、最大粒径为20μm、平均粒径为12μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,在第4周仅烧结体表面崩解为粉末状。而且,在真空包装中经过10个月,观察到表面的粉末化。可以确认,在Zr的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为○。
(实施例13)
实施例13的复合氧化物烧结体,以金属换算,ZrO2按Zr换算含有25摩尔%。碳含量为23ppm、氢15ppm、相对密度为98%、最大粒径为19μm、平均粒径为11μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年也未观察到表面的粉末化。可以确认,在Zr的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例14)
实施例14的复合氧化物烧结体,以金属换算,ZrO2按Zr换算含有48摩尔%。碳含量为73ppm、氢65ppm、相对密度为99%、最大粒径为17μm、平均粒径为3μm。此时,该复合氧化物烧结体的密度高,但是,碳、氢含量多,粒径也小。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。但是,测定表面硬度发现有降低一些的倾向。而且,在真空包装中,经过一年,逐渐观察到表面的粉末化。
可以确认,在Zr的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有显著的抑制崩解的效果。评价为◎。
(实施例15)
实施例15的复合氧化物烧结体,以金属换算,TiO2按Ti换算含有1摩尔%。碳含量为37ppm、氢30ppm、相对密度为95%、最大粒径为40μm、平均粒径为10μm。此时,该复合氧化物烧结体的氧量、氢量多,另外相对密度低一些,为95%
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,在第4周烧结体崩解为粉末状。而且,在真空包装中,经过6个月,观察到表面的粉末化。可以确认,该复合氧化物烧结体通过Ti的存在以及其它附加因素,具有抑制崩解的效果。评价为○。
(实施例16)
实施例16的复合氧化物烧结体,以金属换算,TiO2按Ti换算含有10摩尔%。碳含量为25ppm、氢21ppm、相对密度为98%、最大粒径为28μm、平均粒径为13μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。
可以确认,在Ti的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例17)
实施例17的复合氧化物烧结体,以金属换算,TiO2按Ti换算含有30摩尔%。碳含量为25ppm、氢21ppm、相对密度为98%、最大粒径为28μm、平均粒径为13μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,与实施例16同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在Ti的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例18)
实施例18的复合氧化物烧结体,以金属换算,TiO2按Ti换算含有49摩尔%。碳含量为19ppm、氢25ppm、相对密度为97%、最大粒径为20μm、平均粒径为11μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,与实施例17同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。
可以确认,在Ti的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例19)
实施例19的复合氧化物烧结体,以金属换算,TiO2和ZrO2比为1∶1,按Ti和Zr的金属换算,含有10摩尔%。碳含量为20ppm、氢23ppm、相对密度为97%、最大粒径为19μm、平均粒径为9μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,与实施例18同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在包含Ti和Zr的金属的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例20)
实施例19的复合氧化物烧结体,以金属换算,TiO2和ZrO2比为1∶1,按Ti和Zr的金属换算,含有30摩尔%。碳含量为17ppm、氢18ppm、相对密度为97%、最大粒径为26μm、平均粒径为15μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,与实施例19同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在包含Ti和Zr的金属的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例21)
实施例21的复合氧化物烧结体,以金属换算,TiO2和HfO2比为1∶1,按Ti和Hf的金属换算,含有20摩尔%。碳含量为18ppm、氢19ppm、相对密度为97%、最大粒径为23μm、平均粒径为12μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,与实施例20同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在包含Ti和Hf的金属的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例22)
实施例22的复合氧化物烧结体,以金属换算,TiO2和HfO2比为1∶1,按Ti和Hf的金属换算,含有40摩尔%。碳含量为25ppm、氢20ppm、相对密度为97%、最大粒径为23μm、平均粒径为17μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,实施例21同样,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在包含Ti和Hf的金属的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(实施例23)
实施例23的复合氧化物烧结体,以金属换算,TiO2、ZrO2和HfO2之比为1∶1∶1,按Ti、Zr和Hf的金属换算,含有6摩尔%。碳含量为53ppm、氢37ppm、相对密度为96%、最大粒径为48μm、平均粒径为3μm。此时,该复合氧化物烧结体除了碳含量、氢含量显著高、平均粒径小的方面以外,所有条件均符合本申请发明。
结果,在作为加速试验恒温(40℃)、恒湿(湿度90%)槽中,在第4周烧结体崩解为粉末状。另外,在真空包装中经过6个月,观察到表面的粉末化。该复合氧化物烧结体的评价为○。
(实施例24)
实施例24的复合氧化物烧结体,以金属换算,TiO2、ZrO2和HfO2之比为1∶1∶1,按Ti、Zr和Hf的金属换算,含有24摩尔%。碳含量为23ppm、氢24ppm、相对密度为97%、最大粒径为23μm、平均粒径为16μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,该复合氧化物烧结体在包含Ti、Zr和Hf的金属的存在以及其它附加因素符合本申请发明的条件的情况下,具有抑制崩解的效果。评价为◎。
(实施例25)
实施例25的复合氧化物烧结体,以金属换算,TiO2、ZrO2和HfO2之比为1∶1∶1,按Ti、Zr和Hf的金属换算,含有45摩尔%。碳含量为23ppm、氢24ppm、相对密度为97%、最大粒径为28μm、平均粒径为15μm。此时,该复合氧化物烧结体的所有条件均符合本申请发明。
结果,在作为加速试验的恒温(40℃)、恒湿(湿度90%)槽中,即使在第8周,也未观察到烧结体的粉末状崩解。而且,在真空包装中,即使经过一年,也未观察到粉末化。可以确认,在包含Ti、Zr和Hf的金属的存在以及其它附加因素符合本申请发明的条件的情况下,该复合氧化物烧结体具有抑制崩解的效果。评价为◎。
(比较例1)
该比较例1的氧化物烧结体是La2O3。碳含量为31ppm、氢27ppm、相对密度为96%,最大粒径和平均粒径不能测定。此时,在大气中放置两周,崩解为白色的粉末状。此时不能保持烧结体的形状。评价为×。以上的结果如表1所示。
产业实用性
将氧化镧烧结体溅射靶在大气中长时间放置时,由于潮解性而与水分反应从而成为由氢氧化物的白色粉末覆盖的状态,产生不能进行正常的溅射的问题。另外,吸收大气中的二氧化碳而崩解为碳酸镧粉末。本发明的靶可以延迟这些问题的产生,具有能够保存至实际应用上没有问题的期限的显著效果,特别是作为能够高效且稳定地提供High-K栅绝缘膜用氧化物的氧化镧基烧结体、包含该烧结体的溅射靶、氧化镧基烧结体的制造方法及通过该制造方法制造溅射靶的方法是有用的。
Claims (6)
1.一种包含氧化镧基烧结体的溅射靶,含有氧化钛、氧化锆、氧化铪的一种或两种以上,其余为氧化镧和不可避免的杂质,其特征在于,相对于烧结体中的金属元素的合计成分量,钛、锆、铪的金属元素的量为1摩尔%以上且低于50摩尔%,氢和碳各自为25重量ppm以下,相对密度为96%以上,最大粒径为50μm以下,平均粒径为5μm以上。
2.一种包含氧化镧基烧结体的溅射靶的制造方法,其特征在于,使用La2(CO3)3粉末或La2O3粉末作为氧化镧原料粉末,使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物,将其以相对于金属La与添加氧化物中的金属成分钛、锆、铪的总合计量,添加氧化物中的金属成分钛、锆、铪的合计量为1摩尔%以上且低于50摩尔%的方式进行配合并混合后,将该混合粉末在大气中进行加热合成,然后将该合成材料粉碎得到粉末,然后将该合成粉末进行热压得到烧结体。
3.如权利要求1所述的包含氧化镧基烧结体的溅射靶的制造方法,其特征在于,使用La2(CO3)3粉末或La2O3粉末作为氧化镧原料粉末,使用TiO2、ZrO2、HfO2粉末的一种或两种以上作为添加氧化物,将其以添加氧化物的金属成分相对于La的组成比为规定值的方式进行配合并混合后,将该混合粉末在大气中进行加热合成,然后将该合成材料粉碎得到粉末,然后将该合成粉末进行热压得到烧结体。
4.如权利要求2或3所述的包含氧化镧基烧结体的溅射靶的制造方法,其特征在于,混合通过湿式球磨机进行,合成在大气中、在1350℃~1550℃下加热5小时~25小时来制造。
5.如权利要求2或3所述的包含氧化镧基烧结体的溅射靶的制造方法,其特征在于,热压在1200℃~1500℃下、真空中进行1小时~5小时。
6.如权利要求4所述的包含氧化镧基烧结体的溅射靶的制造方法,其特征在于,热压在1200℃~1500℃下、真空中进行1小时~5小时。
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EP2298715A4 (en) | 2011-11-23 |
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