CN105555997B - 钽溅射靶及其制造方法 - Google Patents
钽溅射靶及其制造方法 Download PDFInfo
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- CN105555997B CN105555997B CN201580001927.XA CN201580001927A CN105555997B CN 105555997 B CN105555997 B CN 105555997B CN 201580001927 A CN201580001927 A CN 201580001927A CN 105555997 B CN105555997 B CN 105555997B
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 95
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 230000005611 electricity Effects 0.000 claims abstract description 14
- 238000001953 recrystallisation Methods 0.000 claims abstract description 14
- 238000005266 casting Methods 0.000 claims abstract description 6
- 238000003723 Smelting Methods 0.000 claims abstract description 5
- 238000004544 sputter deposition Methods 0.000 claims description 53
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 150000004767 nitrides Chemical class 0.000 claims description 22
- 238000009792 diffusion process Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 103
- 230000009467 reduction Effects 0.000 description 17
- 238000005242 forging Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- 238000005096 rolling process Methods 0.000 description 14
- 238000005097 cold rolling Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000005477 sputtering target Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 230000003628 erosive effect Effects 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 230000008676 import Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010273 cold forging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000009497 press forging Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 241001424392 Lucia limbaria Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010409 thin film Substances 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
- B22D21/06—Casting non-ferrous metals with a high melting point, e.g. metallic carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/02—Use of electric or magnetic effects
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0247—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
- C21D8/0273—Final recrystallisation annealing
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/0062—Heat-treating apparatus with a cooling or quenching zone
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
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- C—CHEMISTRY; METALLURGY
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
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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
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
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- H01J37/32—Gas-filled discharge tubes
- H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
- H01J37/3488—Constructional details of particle beam apparatus not otherwise provided for, e.g. arrangement, mounting, housing, environment; special provisions for cleaning or maintenance of the apparatus
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- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
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- H01L21/02266—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by physical ablation of a target, e.g. sputtering, reactive sputtering, physical vapour deposition or pulsed laser deposition
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by physical means, e.g. sputtering, evaporation
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
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- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
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- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
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- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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Abstract
一种钽溅射靶,其特征在于,钽溅射靶的溅射面的(100)面的取向率为30%~90%且(111)面的取向率为50%以下。一种钽溅射靶的制造方法,其特征在于,对经熔炼铸造的钽锭进行锻造和再结晶退火,然后进行轧制和热处理,从而形成钽溅射靶的(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶体组织。通过控制靶的晶体取向,具有以下效果:使钽靶的预烧累计电量减少,容易产生等离子体,使成膜速度稳定,并且使膜的电阻变动减小。
Description
技术领域
本发明涉及钽溅射靶及其制造方法。特别是涉及用于形成作为大规模集成电路(LSI)中的铜布线的扩散阻挡层的Ta膜或TaN膜的钽溅射靶及其制造方法。
背景技术
以往,使用铝作为半导体元件的布线材料,但随着元件的微细化、高集成化,出现布线延迟的问题,逐渐使用电阻小的铜代替铝。虽然铜作为布线材料非常有效,但是由于铜本身是活跃的金属,因此存在扩散至层间绝缘膜而导致污染的问题,在铜布线与层间绝缘膜之间需要形成Ta膜、TaN膜等扩散阻挡层。
一般而言,Ta膜、TaN膜通过使用钽靶进行溅射来成膜。到目前为止,关于钽靶,关于对溅射时的性能造成的影响,已知靶中含有的各种杂质、气体成分、晶面取向、晶粒尺寸等对成膜速度、膜厚的均匀性、粉粒产生等造成影响。
例如,在专利文献1中,记载了通过形成从靶厚度的30%的位置向靶的中心面(111)取向占优的晶体组织,使膜的均匀性提高。
另外,专利文献2中,记载了通过使钽靶的晶体取向随机(不对齐于特定的晶体取向),成膜速度增大,并且使膜的均匀性提高。
另外,在专利文献3中,记载了通过在溅射面中选择性地增加原子密度高的(110)、(100)、(211)的面取向,成膜速度提高,并且通过抑制面取向的变动,均匀性提高。
此外,专利文献4中,记载了通过将利用X射线衍射求出的(110)面的强度比的、根据溅射表面部分的位置不同而产生的变动调节为20%以内,使膜厚均匀性提高。
另外,在专利文献5中,记述了通过将模锻、挤出、旋转锻造、无润滑的镦锻与多向轧制组合使用,可以制作出具有非常强的(111)、(100)等晶体学织构的圆形金属靶。
除此以外,在下述专利文献6中,记载了对钽锭实施锻造、退火、轧制加工,最终组成加工后,进一步在1173K以下的温度下进行退火,使未再结晶组织为20%以下、90%以下的钽溅射靶的制造方法。
另外,在专利文献7中公开了下述技术:通过锻造、冷轧等加工和热处理,使靶的溅射面的峰的相对强度为(110)>(211)>(100),从而使溅射特性稳定。一般而言,(110)由于加工应变而变高,因此这样加工的表面的溅射速度变快,通过预烧(burn-in)进行的表层除去快速结束,具有加快稳定区域的露出的效果,因此具有采用这样的(110)的倾向。
此外,在专利文献8中,记载了对钽锭进行锻造,在该锻造工序中进行2次以上的热处理,然后实施冷轧,并进行再结晶热处理。
另外,在专利文献9中,记载了一种钽溅射靶,其特征在于,含有1质量ppm以上且100质量ppm以下的钼作为必要成分,除了钼和气体成分以外的纯度为99.998%以上。上述记载的钽溅射靶,其特征在于,还含有0~100质量ppm(其中,不包括0质量ppm)的铌,除了钼、铌和气体成分以外的纯度为99.998%以上。记载了得到具有均匀微细的组织、等离子体稳定、膜的均匀性(uniformity)优良的高纯度钽溅射靶。
另外,在专利文献10中,记载了一种钽溅射靶,其特征在于,含有1质量ppm以上且100质量ppm以下的钨作为必要成分,除了钨和气体成分以外的纯度为99.998%以上。上述钽溅射靶,其特征在于,还含有0~100质量ppm(其中,不包括0质量ppm)的钼和/或铌,钨、钼、铌的合计含量为1质量ppm以上且150质量ppm以下,除了钨、钼、铌和气体成分以外的纯度为99.998%以上。记载了得到具有均匀微细的组织、等离子体稳定、膜的均匀性(uniformity)优良的高纯度钽溅射靶。
关于用于半导体的钽溅射靶,如上所述正在开发多种类型的靶。靶材主要采用约10mm的厚度,通过增加每1块靶的成膜数(晶片数)而实现降低成本。此时,增加靶的厚度能够降低靶的更换频率,减少装置的停止时间,因此可以说对于降低成本是有效的。
为了增加靶的使用累计时间,只要增加靶的厚度、能够更长期地使用即可,然而在钽靶的情况下存在特有的问题。一般而言,在靶的溅射时,有时在晶片周围设备上形成被膜,或者由于反向溅射而在靶周围形成被膜。
因此,采用在靶的使用过程中将溅射装置(真空设备)向大气开放,更换被污染的设备,然后再次开始溅射的方法,由此实现成膜的延长。
但是,在高真空中进行溅射后的钽靶,露出非常活化的表面,在将真空设备向大气开放,并将靶暴露于大气时,会快速形成牢固的氧化膜。这样的氧化膜的形成是即使不特意地引入氧气、由大气中的氧气也会引起的现象。
形成有这样的氧化膜的钽靶,即使想要再次进行抽真空,并重新开始溅射,也会产生以下问题:表面的氧化膜使成膜特性不稳定,成膜速度混乱,并且将该表面氧化膜通过溅射除去而使稳定的靶新生面露出的预烧时间变长。其结果是,导致时间与电力、材料的浪费及材料(成膜)特性劣化。
但是,在上述说明的一系列专利文献中,未公开解决该问题的方法,甚至不能找到一点线索。
现有技术文献
专利文献
专利文献1:日本特开2004-107758号公报
专利文献2:国际公开2005/045090号
专利文献3:日本特开平11-80942号公报
专利文献4:日本特开2002-363736号公报
专利文献5:日本特表2008-532765号公报
专利文献6:日本专利第4754617号
专利文献7:国际公开2011/061897号
专利文献8:日本专利第4714123号
专利文献9:国际公开2011/018970号
专利文献10:国际公开2011/08971号
发明内容
发明所要解决的课题
本发明中,在钽溅射靶中,控制靶的溅射面的晶体取向,从而使氮化膜的形成变得容易,在采用在靶的使用过程中,将溅射装置(真空设备)向大气开放,更换被污染的设备,然后再次开始溅射的方法时,存在的问题是,钽靶的活化的表面直接暴露于大气时,会形成牢固的氧化膜。
因此,本申请发明中,事先形成氮化膜。即,在向大气开放前,在钽靶的表面上形成氮化膜。由此,可以有效地抑制由于与空气中的氧气的快速反应而形成氧化膜。而且,可以使成膜特性和成膜速度稳定,并且能够缩短预烧时间,能够改善时间与电力的浪费及材料(成膜)特性。
此外,能够增加靶的使用累计时间,能够增加靶的厚度,并且能够更长期地使用靶,对于降低成本是有效的。由此,能够提供对于形成包含Ta膜或TaN膜等的扩散阻挡层有用的、有效的钽溅射靶。
用于解决课题的手段
为了解决上述的课题,本发明提供以下的发明。
1)一种钽溅射靶,其特征在于,钽溅射靶的溅射面的(100)面的取向率为30%~90%且(111)面的取向率为50%以下。
2)根据上述1)所述的钽溅射靶,其特征在于,在钽溅射靶的溅射面上具有氮化膜。
3)根据上述2)所述的钽溅射靶,其特征在于,氮化膜的厚度为以上。
4)一种扩散阻挡层用薄膜,其通过使用上述1)~3)中任一项所述的钽溅射靶而形成。
5)根据上述4)所述的通过使用钽溅射靶而形成的扩散阻挡层用薄膜,其特征在于,溅射膜的电阻变动为15%以下。
6)根据上述4)~5)中任一项所述的通过使用钽溅射靶而形成的扩散阻挡层用薄膜,其特征在于,预烧累计电量为100千瓦时以下。
7)一种半导体器件,其具有上述4)~6)中任一项所述的扩散阻挡层用薄膜。
另外,本发明提供以下的发明。
8)一种钽溅射靶的制造方法,其特征在于,对经熔炼铸造的钽锭进行锻造和再结晶退火,然后进行轧制和热处理,从而形成钽溅射靶的(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶体组织。
9)根据上述8)所述的钽溅射靶的制造方法,其特征在于,对于预定再使用于溅射的靶,暂时停止溅射操作,在将真空容器向大气开放前,将氮气供给至该靶的表面,从而形成氮化膜。
10)根据上述9)所述的钽溅射靶的制造方法,其中,形成的氮化膜的厚度为以上。
发明效果
本发明的钽溅射靶通过控制靶的溅射面的晶体取向,可以容易地在钽靶表面上形成氮化膜。由此,在采用在靶的使用过程中,将溅射装置(真空设备)向大气开放,更换被污染的设备,然后再次开始溅射的方法时,即使在钽靶的活化的表面暴露于大气中的情况下,也能够抑制牢固的氧化膜的形成,使成膜特性和成膜速度稳定,并且能够缩短预烧时间,能够改善时间与电力的浪费及材料(成膜)特性。
其结果是,能够增加靶的厚度,能够增加靶的使用累计时间,并且能够更长期地使用靶,因此,对于靶的使用成本的降低是极其有效的。由此,能够提供对于形成包含Ta膜或TaN膜等的扩散阻挡层有用的、有效的钽溅射靶。
需要说明的是,预烧累计电量为由预烧时的输入功率kW乘以溅射时间h而得到的千瓦时(kWh)表示的电量。通常,在溅射装置中,对输入功率、溅射时间进行管理,因此,对溅射通常基本上通过累计电量进行管理。
具体实施方式
本发明的钽溅射靶利用通常的工序实施溅射,但具体以下特征:在靶的使用过程中,将溅射装置(真空设备)向大气开放,更换被污染的设备,然后再次开始溅射时,本申请发明的具有(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶面取向率的钽溅射靶容易利用氮气形成氮化膜。
而且,事先形成的氮化膜可以有效地抑制由于与空气中的氧气的快速反应而导致的氧化膜的形成,因此可以解决以往的问题。
需要说明的是,本申请发明的具有(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶面取向率的钽溅射靶,作为钽靶,具有特殊的取向,因此其本身可以称为具有新颖性的钽靶。钽靶通常具有5mm以上的厚度。
因此,根据上述情况,对于预定再使用于溅射的靶,暂时停止溅射操作,在将真空容器向大气开放前,将氮气供给至该靶的表面,从而形成氮化膜,并将氮化膜的厚度设定为以上。
在形成氮化膜时,对于预定再使用于溅射的靶,可以暂时停止溅射操作,在将真空容器向大气开放前,将氮气供给至该靶的表面,从而形成氮化膜。
溅射装置独立地具有N2和Ar的供给线,但该操作的目的在于表面的氮化,不进行溅射,不需要Ar混合气体,因此仅供给氮气。根据需要,也可以使用含有N2(Ar 1%)的气体。
在更换被污染的设备然后再次开始溅射时,在表面上具有氮化膜的钽溅射靶的氮化膜具有以下特征,可以有效地抑制氧化膜的形成,并且再使用时的预烧时间可以为比较短的时间。因此,可以减少时间与电力的消耗及由于预烧而消失的材料,并且具有改善成膜特性的效果。其结果是,能够增加钽靶的厚度,能够增加靶的使用累计时间,并且能够更长期地使用靶,因此可以说对于靶的使用成本的降低是极其有效的。
由此,能够使再使用时的钽溅射膜的电阻变动为使用中断前的15%以下,而且能够得到100千瓦时以下的预烧累计电量。这样的扩散阻挡层用薄膜对于制作半导体器件是有效的。需要说明的是,电阻变动通过比较溅射装置向大气开放前后的成膜晶片的薄层电阻而得到,优选向大气开放后的薄层电阻落入向大气开放前的薄层电阻值的85%~115%的范围内。
为了形成钽溅射靶的(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶体组织,可以如下进行制造:对经熔炼铸造的钽锭,在至少重复锻造-退火的循环2次以上、优选3次以上的条件下,进行锻造和再结晶退火,然后进行轧制和热处理。需要说明的是,所述(100)面或(111)面包含自靶表面至内部、自溅射初期至溅射结束露出的全部的部位。
本发明的钽溅射靶可以用于形成铜布线中的Ta膜或TaN膜等扩散阻挡层。在通过将氮气导入至溅射时的气氛中而形成TaN膜的情况下,本发明的溅射靶通过控制靶的溅射面的晶体取向,具有以下优良效果:降低钽靶的放电电压,容易产生等离子体,并且能够提高等离子体的稳定性,因此在具有该Ta膜或TaN膜等扩散阻挡层的铜布线的形成、进而具有该铜布线的半导体器件的制造中能够提高制品成品率。
本发明的钽溅射靶通过以下工序制造。如果示出其例子,首先,通常使用4N(99.99%)以上的高纯度钽作为钽原料。将其通过电子束熔炼等进行熔炼,并对其进行铸造而制作锭或坯。接着,对该锭或坯进行锻造、再结晶退火。具体而言,例如,进行锭或坯-压锻(締め鍛造)-1100~1400℃的温度下的退火-冷锻(一次锻造)-再结晶温度~1400℃的温度下的退火-冷锻(二次锻造)-再结晶温度~1400℃的温度下的退火。
接着,进行冷轧。通过调节该冷轧的条件,可以控制本发明的钽溅射靶的取向率。具体而言,关于轧辊,可以使用辊径小的轧辊,优选为500mmφ以下。另外,轧制速度尽可能慢,优选为10m/分钟以下。此外,在仅实施1次轧制的情况下,压下率优选高达超过80%,在重复进行2次以上轧制的情况下,压下率设定为60%以上,需要使靶的最终厚度与轧制1次的情况相同。优选压下率总计超过80%。另外,设计使得轧制1道次的压下率不超过10%。
接着,进行热处理。通过与冷轧条件一起调节在冷轧后进行的热处理条件,可以控制本发明的钽溅射靶的取向率。具体而言,热处理温度越高越好,优选设定为800℃~1200℃。虽然也取决于通过轧制而引入的应变的量,但是为了得到再结晶组织,需要在800℃以上的温度下进行热处理。另一方面,在超过1200℃下热处理会促进粗大晶粒生长,并且在经济上是不优选的。然后,通过对靶的表面进行机械加工、抛光加工等精加工而得到最终的制品。
通过上述的制造工序制造钽靶,但是本发明中特别重要的是,在靶的溅射面的晶体取向中,提高(100)面的取向率,并且降低(111)面的取向率。
与取向的控制显著相关的主要是轧制工序。在轧制工序中,通过控制轧辊直径、轧制速度、压下率等参数,能够改变轧制时引入的应变的量、分布,从而能够控制(100)面的取向率和(111)面的取向率。
为了有效地进行面取向率的调节,需要一定程度的重复的条件设定,但是一旦能够调节(100)面的取向率和(111)面的取向率,则通过设定该制造条件,能够制造恒定的特性的(具有固定水平的特性)靶。
在制造具有本发明的取向特性的靶时,使用轧辊直径500mm以下的轧辊,将轧制速度设定为10m/分钟以下,并将1道次的压下率设定为10%以下是有效的。但是,只要是能够实现本发明的晶体取向的制造工序,未必需要仅限定于该制造工序。在一系列的加工中,有效的条件设定是,通过锻造·轧制破坏铸造组织,并且充分进行再结晶化。
此外,优选在对经熔炼铸造的钽锭或坯实施锻造、轧制等加工后,进行再结晶退火,使组织微细且均匀化。
实施例
接下来,基于实施例说明本发明。以下所示的实施例是为了便于理解,并不是用这些实施例限制本发明。即,基于本发明的技术构思的变形和其它实施例当然也包含在本发明中。
对纯度99.995%的钽原料进行电子束熔炼,并对其进行锻造从而制成直径195mmφ的锭。接着,在室温下对该锭进行压锻而制成直径150mmφ,然后在1100℃~1400℃的温度下对其进行再结晶退火。
再次,在室温下对其重复进行拔长锻造(鍛伸)-墩锻而制成厚度100mm、直径150mmφ(一次锻造),并在再结晶温度~1400℃的温度下对其进行再结晶退火。然后,在室温下对其重复进行拔长锻造-墩锻而制成厚度70mm~100mm、直径150mm~185mmφ(二次锻造),并在再结晶温度~1400℃的温度下对其进行再结晶退火,从而得到靶材。
(实施例1)
实施例1中,对于得到的靶材,使用轧辊直径400mm的轧辊,设定轧制速度为10m/分钟、压下率为86%、1道次的最大压下率为10%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在1000℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为30%且(111)面的取向率为50%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气60秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量少至75千瓦时,能够在短时间内溅射,并且溅射后的膜的电阻变动为14%,膜特性的变化少。
钽膜的成膜在下述条件下进行(以下的实施例、比较例也同样)。
<成膜条件>
电源:直流方式
功率:15kW
极限真空度:5×10-8托
气氛气氛组成:Ar
溅射气体压力:5×10-3托
溅射时间:15秒
(实施例2)
实施例2中,对于得到的靶材,使用轧辊直径400mm的轧辊,设定轧制速度为8m/分钟、压下率为88%、1道次的最大压下率为10%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在900℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为50%且(111)面的取向率为20%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气60秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量少至50千瓦时,能够在短时间内溅射,并且溅射后的膜的电阻变动为10%,膜特性的变化少。
(实施例3)
实施例3中,对于得到的靶材,使用轧辊直径400mm的轧辊,设定轧制速度为5m/分钟、压下率为85%、1道次的最大压下率为10%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在1100℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为70%且(111)面的取向率为15%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气60秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量少至35千瓦时,能够在短时间内溅射,并且溅射后的膜的电阻变动为7%,膜特性的变化少。
(实施例4)
实施例4中,对于得到的靶材,使用轧辊直径500mm的轧辊,设定轧制速度为5m/分钟、压下率为90%、1道次的最大压下率为5%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在800℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为90%且(111)面的取向率为5%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气60秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量少至25千瓦时,能够在短时间内溅射,并且溅射后的膜的电阻变动为5%,膜特性的变化少。
(比较例1)
比较例1中,对于得到的靶材,使用轧辊直径400mm的轧辊,设定轧制速度为5m/分钟、压下率为85%、1道次的最大压下率为10%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在1100℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为70%且(111)面的取向率为15%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量少至300千瓦时,能够在短时间内溅射,并且溅射后的膜的电阻变动为35%,膜特性的变化最大。认为这是因为未形成氮化膜,氧化快速进行。
(比较例2)
比较例2中,对于得到的靶材,使用轧辊直径500mm的轧辊,设定轧制速度为15m/分钟、压下率为78%、1道次的最大压下率为15%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在800℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为20%且(111)面的取向率为60%的晶体组织的钽溅射靶。需要说明的是,该晶体取向偏离本申请发明。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气60秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量增加至275千瓦时,在达到恒定的溅射之前需要较长时间。而且溅射后的膜的电阻变动为32%,膜特性的变化大,得到不优选的结果。认为这是因为,晶体取向率不合适。
(比较例3)
比较例3中,对于得到的靶材,使用轧辊直径400mm的轧辊,设定轧制速度为5m/分钟、压下率为85%、1道次的最大压下率为10%,进行冷轧,从而制成厚度14mm、直径520mmφ,并对其在1100℃的温度下进行热处理。然后,对表面进行切削、抛光而制成靶。
通过以上的工序,可以得到具有(100)面的取向率为70%且(111)面的取向率为15%的晶体组织的钽溅射靶。使用该溅射靶实施溅射。
接着,在靶的侵蚀最深部厚度达到约8mm时,暂时停止溅射,向溅射装置(真空容器)内导入氮气30秒。由此,在靶的表面上形成厚度为约的氮化膜。
接着,将溅射装置向大气开放,实施内部的设备的更换或清洗。然后,再次密闭溅射装置,并重新开始溅射。预烧的电量增加至105千瓦时。在能够进行恒定的溅射之前需要较长时间。而且溅射后的膜的电阻变动为24%,膜特性的变化大。认为这是因为,用于形成氮化膜的氮气流动时间不足。
如以上的实施例和比较例所示,处于本申请发明的条件的范围内的方案,使钽靶的成膜特性及成膜速度稳定,并且能够缩短预烧时间,能够改善时间与电力的浪费及材料(成膜)特性。另外,具有能够将放电电压的变动抑制得低,进而能够降低放电异常发生率的优良效果。
产业实用性
本发明提供钽溅射靶,通过控制靶的溅射面的晶体取向,能够容易地在钽靶表面形成氮化膜。由此,在靶的使用过程中,在采用将溅射装置(真空设备)向大气开放,更换被污染的设备然后再次开始溅射的方法时,即使在钽靶的活化的表面暴露于大气中的情况下,也能够抑制牢固的氧化膜的形成,使成膜特性及成膜速度稳定,并且能够缩短预烧时间,能够改善时间与电力的浪费及材料(成膜)特性。其结果是,能够增加靶的厚度,能够增加靶的使用累计时间,并且能够更长期地使用靶,因此对于靶的使用成本的降低是极其有效的。由此,能够提供对于形成包含Ta膜或TaN膜等的扩散阻挡层有用的、有效的钽溅射靶。
Claims (8)
1.一种钽溅射靶,其特征在于,钽溅射靶的溅射面的(100)面的取向率为30%~90%且(111)面的取向率为50%以下,在钽溅射靶的溅射面上具有氮化膜。
2.根据权利要求1所述的钽溅射靶,其特征在于,氮化膜的厚度为以上。
3.一种扩散阻挡层用薄膜,其通过使用权利要求1~2中任一项所述的钽溅射靶而形成。
4.根据权利要求3所述的通过使用钽溅射靶而形成的扩散阻挡层用薄膜,其特征在于,溅射膜的电阻变动为15%以下。
5.根据权利要求3~4中任一项所述的通过使用钽溅射靶而形成的扩散阻挡层用薄膜,其特征在于,预烧累计电量为100千瓦时以下。
6.一种半导体器件,其具有权利要求3~5中任一项所述的扩散阻挡层用薄膜。
7.一种钽溅射靶的制造方法,其特征在于,对经熔炼铸造的钽锭进行锻造和再结晶退火,然后进行轧制和热处理,从而形成钽溅射靶的(100)面的取向率为30%~90%且(111)面的取向率为50%以下的晶体组织,
对于预定再使用于溅射的靶,暂时停止溅射操作,在将真空容器向大气开放前,将氮气供给至该靶的表面,从而形成氮化膜。
8.根据权利要求7所述的钽溅射靶的制造方法,其中,氮化膜的厚度为以上。
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WO2014097897A1 (ja) | 2012-12-19 | 2014-06-26 | Jx日鉱日石金属株式会社 | タンタルスパッタリングターゲット及びその製造方法 |
WO2014136679A1 (ja) | 2013-03-04 | 2014-09-12 | Jx日鉱日石金属株式会社 | タンタルスパッタリングターゲット及びその製造方法 |
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WO2016190160A1 (ja) | 2015-05-22 | 2016-12-01 | Jx金属株式会社 | タンタルスパッタリングターゲット及びその製造方法 |
SG11201708112TA (en) | 2015-05-22 | 2017-11-29 | Jx Nippon Mining & Metals Corp | Tantalum sputtering target, and production method therefor |
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WO2018179742A1 (ja) * | 2017-03-30 | 2018-10-04 | Jx金属株式会社 | タンタルスパッタリングターゲット |
WO2021206169A1 (ja) * | 2020-04-10 | 2021-10-14 | ローム株式会社 | サーマルプリントヘッド及びその製造方法並びにサーマルプリンタ |
CN115044876A (zh) * | 2022-06-02 | 2022-09-13 | 有研亿金新材料有限公司 | 一种小尺寸高性能钽靶坯的制备方法 |
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