CN108987262B - 硼膜的除去方法和硼膜的图案形成方法 - Google Patents
硼膜的除去方法和硼膜的图案形成方法 Download PDFInfo
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- CN108987262B CN108987262B CN201810602823.XA CN201810602823A CN108987262B CN 108987262 B CN108987262 B CN 108987262B CN 201810602823 A CN201810602823 A CN 201810602823A CN 108987262 B CN108987262 B CN 108987262B
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- 229910052796 boron Inorganic materials 0.000 title claims abstract description 182
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000000059 patterning Methods 0.000 title description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 230000001590 oxidative effect Effects 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- 150000002500 ions Chemical class 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000007789 gas Substances 0.000 claims description 51
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 8
- 238000004093 laser heating Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000000206 photolithography Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 description 203
- 229910052810 boron oxide Inorganic materials 0.000 description 37
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 37
- 235000012431 wafers Nutrition 0.000 description 30
- 239000000126 substance Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000001312 dry etching Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000009832 plasma treatment Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- JPYPZXAFEOFGSM-UHFFFAOYSA-N O.[B]=O Chemical compound O.[B]=O JPYPZXAFEOFGSM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl boron Chemical compound 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H01L21/02351—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to corpuscular radiation, e.g. exposure to electrons, alpha-particles, protons or ions
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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
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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
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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
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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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/02255—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by thermal treatment
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- Computer Hardware Design (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
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- Cleaning Or Drying Semiconductors (AREA)
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- Semiconductor Memories (AREA)
Abstract
本发明提供能够容易地除去硼膜并且能够局部选择性地除去微小部分的硼膜的除去方法和能够形成硼膜的微小图案的图案形成方法。包括:在氧化气氛下对通过CVD形成于基片上的硼膜整体地或者局部地进行热处理,使经过热处理的部分氧化的步骤;和利用水或者含有电解质离子的水溶液对硼膜的被氧化的部分进行除去的步骤。
Description
技术领域
本发明涉及硼膜的除去方法和硼膜的图案形成方法。
背景技术
近年来,随着半导体技术的发展,半导体装置向微小化发展,出现了10nm以下的半导体装置。另外,为了进一步实现半导体装置的集成化,发展出立体地构筑半导体元件的技术。因此,在半导体晶片上形成的薄膜的层叠数增加,在例如使用了三维NAND的闪存中,需要利用干法蚀刻对包含氧化硅(SiO2)膜或氮化硅(SiN)膜等、厚度为1μm以上的较厚的层叠膜进行微小加工。
作为用于进行微小加工的硬掩模,现有技术中使用非晶硅膜或者非晶碳膜,但是它们的蚀刻耐受性低。因此,对于使用这些膜作为硬掩模的情况,必须使膜厚加厚,需要形成1μm以上的较厚的膜。
另外,作为下一代的硬掩模材料,研究了蚀刻耐受性高于非晶硅膜或者非晶碳膜的钨等的金属材料膜。然而,对蚀刻耐受性非常高的钨膜等的金属材料膜而言,难以应对干法蚀刻加工后的剥离或者金属污染等。
因此,关于与非晶硅膜或者非晶碳膜相比干法蚀刻耐受性高并且相对于SiO2膜等具有高选择比的新型硬掩模材料,对硼膜进行了研究。专利文献1记载了一种通过CVD对作为硬掩模的硼膜进行成膜的技术。
对于作为硬掩模而形成的膜而言,在这样的情况下需要进行除去处理,即当为了将被蚀刻膜蚀刻为规定形状,局部地进行除去以加工为规定的微小图案的情况,当对成膜于半导体晶片的端部(边缘、斜面)的膜局部地进行除去的情况,当实现了作为硬掩模的作用后对整体进行除去的情况等等。现有技术中对作为硬掩模材料使用的非晶硅膜或者非晶碳膜,利用O2等离子体进行除去。
然而,硼膜对O2等离子体的耐受性高,利用O2等离子体基本不能除去硼膜。因此,对利用药液进行的除去进行了研究,专利文献1中记载了一种利用含有具有氧化能力的酸的药液,对通过CVD成膜而得的硼膜进行除去的方法。
现有技术文献
专利文献
专利文献1:日本特开2013-533376号公报
发明内容
发明想要解决的技术问题
然而,对于利用含有具有氧化能力的酸的药液进行除去的情况,难以局部地选择性地除去微小部分。
因此,本发明的课题为提供能够容易地除去硼膜,并且能够局部地选择性地除去微小部分的硼膜的除去方法以及能够形成硼膜的微小图案的图案形成方法。
用于解决技术问题的技术方案
为解决上述技术问题,本发明的第一方面提供一种对通过CVD形成于基片上的硼膜进行除去的硼膜的除去方法,其包括:在氧化气氛下整体或者部分地对上述硼膜进行热处理,使经过热处理的部分氧化的步骤;和利用水或者含有电解质离子的水溶液对上述硼膜的被氧化的部分进行除去的步骤。
本发明的第二方面提供一种在基片上形成硼膜的图案的硼膜的图案形成方法,其包括:通过CVD在基片上形成硼膜的步骤;对上述硼膜在氧化气氛下与规定的图案对应地局部地进行热处理,使经过热处理的部分氧化的步骤;和利用水或者含有电解质离子的水溶液对上述硼膜的被氧化的部分进行除去的步骤。
在上述第一方面和第二方面中,上述氧化气氛可以包含氧或者臭氧。另外,上述电解质离子可以包含H+、NH4 +、F-、Cl-、NO3 -、SO4 2-和OH-中的任一者。上述电解质离子的水溶液优选不包含具有氧化性的酸。
当形成上述硼膜时,能够使用含有硼和氢的原料气体。另外,当形成上述硼膜时,能够使用等离子体CVD。
上述热处理步骤优选在400~1000℃的范围的温度下进行,上述热处理步骤优选进行1~60分钟的时间,上述热处理步骤优选在氧气或者臭氧气体的浓度为20~100%的气氛下进行。
上述热处理步骤能够利用激光加热来进行,能够与规定图案对应地局部地进行加热。另外,上述热处理步骤能够利用灯加热来进行,能够成为形成有规定的抗蚀剂图案的状态,由此对上述硼膜部分局部地进行加热。
上述除去的步骤能够将上述基片浸泡在纯水或者含有电解质离子的水溶液中来进行,此时,优选对浸泡有上述基片的纯水或者含有电解质离子的水溶液施加超声波振动。另外,上述除去的步骤能够通过对上述基片供给纯水或者含有电解质离子的水溶液的水流来进行。
发明效果
根据本发明,对通过CVD形成于基片上的硼膜在氧化气氛进行热处理,由此能够使经过热处理的部分的硼膜局部地成为硼氧化物(加水硼氧化物)。由于该加水硼氧化物具有接近水溶性的性质,因此利用水或者含有电解质离子(H+、NH4 +、F-、Cl-、NO3 -、SO4 2-、OH-等)的水溶液能够容易地除去该加水硼氧化物。因此,能够容易地除去硼膜,并且局部地选择性地除去微小部分。
附图说明
图1是表示本发明的一个实施方式的硼膜除去方法的流程图。
图2是表示CVD硼膜的TDS的结果的图。
图3是用于说明O2热处理前后的硼膜的状态的SEM照片。
图4是用于说明O2等离子体处理前后的硼膜的状态的SEM照片。
图5是表示本发明的一个实施方式的将硼膜除去方法应用于硼膜的图案形成的实施方式的第一例的步骤截面图。
图6是表示本发明的一个实施方式的将硼膜除去方法应用于硼膜的图案形成的实施方式的第二例的步骤截面图。
图7是表示本发明的一个实施方式的将硼膜除去方法应用于晶片端部的硼膜的局部的除去的实施方式的第一例的图。
图8是表示本发明的一个实施方式的将硼膜除去方法应用于晶片端部的硼膜的局部的除去的实施方式的第二例的图。
图9是实验1的样本的硼膜除去处理前后的SEM照片。
图10是形成有PVD硼膜的样本的硼膜除去处理前后的SEM照片。
图11是表示实验2的处理前和在各温度下进行了热处理的处理后的SEM照片的图。
图12是表示处理前和在各温度和各时间下进行了热处理的处理后的SEM照片的图。
附图标记说明
1:硅基片
2:绝缘膜
3:CVD硼膜
4:氧化硼
5、25:抗蚀剂或者掩模材料的膜
11:氧喷嘴
12:激光光源
13:激光
14:灯光源
21:晶片
23:硼膜。
具体实施方式
下面,参照附图,对本发明的实施方式进行说明。
<硼膜的除去方法的概要>
首先,说明本发明的硼膜的除去方法的概要。
硼膜的干法蚀刻耐受性高于现有技术中作为硬掩模使用的非晶硅膜或者非晶碳膜,因此适合做对厚的层叠膜进行蚀刻时的硬掩模。
然而,硼是化学上稳定的物质,干法蚀刻耐受性高,同时也是难以除去的物质,在除去作为现有的硬掩模的非晶硅膜或者非晶碳膜时使用的O2等离子体不能够将其除去。另外,硼膜能够通过氧化药液处理,例如硝酸、硫酸的混合药液处理来除去,但是局部地选择性地除去仍然困难。
因此,对硼膜的除去处理进行研究。
虽然硼是化学上稳定的物质,但是由于氧化硼(加水物)是水溶性(接近水溶性的性质)的,因此若将硼氧化就能够容易地将其除去。可以认为,在实际的氧化硼的药液处理中,能够利用药液形成氧化硼,之后能够通过纯水清洗来除去氧化硼。
与之相反,判断出在干气氛中,即使进行O2等离子体这样的氧化性高的处理也无法形成氧化硼,基本不能除去硼。
进一步进行研究,结果发现:对通过等离子体CVD等的CVD而形成的硼膜而言,使用乙硼烷(B2H6)气体等含有硼和氢的气体作为成膜原料以在膜中含有适当量例如10at%左右的氢,通过在氧化气氛下进行热处理,膜中的氢脱离,在膜中添加氧来生成氧化硼。氧化硼是溶于水的物质,已知利用水能够容易将其除去。
因此,在本发明中,对于形成有使用了含有氢和硼的气体作为成膜原料的CVD硼膜的基片,首先,在包含氧或者臭氧的氧化气氛下实施热处理步骤,之后,实施进行水或者含有电解质离子的水溶液的处理的步骤。由此,能够除去硼膜。即,通过热处理步骤,硼变为氧化硼,通过由水等进行的处理步骤,氧化硼能够被溶解而除去。
<硼膜除去方法的实施方式>
下面,对本发明的一个实施方式的硼膜除去方法进行说明。图1是表示本发明的一个实施方式的硼膜除去方法的流程图。
硼膜作为硬掩模,例如,在形成于硅晶片等的基片上的绝缘膜的上形成。作为硼膜,使用通过CVD成膜得到的膜。通过CVD对硼膜进行成膜时,作为原料气体,能够使用乙硼烷(B2H6)气体、三氯化硼(BCl3)气体与氢的混合气体、三甲基硼(B(CH3)3)气体、三乙基硼(B(C2H5)3)气体这样的烷基硼气体等的、含有硼和氢的气体。另外,原料气体还可以包含Ar气体、He气体等的不活泼气体。另外,对CVD而言,无论是热CVD还是等离子体CVD都可以,但是等离子体CVD更能够获得高密度且优良膜质的膜。在任一情况下,膜中都含有来自原料气体的氢。在CVD成膜时,膜中含有的氢量为大约3.9~11.7at%的范围,实测值为10at%左右。
在本实施方式中,首先,在包含氧或者臭氧等的氧化气氛下对这样的硼膜的整体或者部分(局部)进行热处理,以使硼膜氧化(步骤1)。此时的加热方法没有特殊限制,能够根据硼膜的除去目的使用适当的方法。
例如,对硼膜整体进行除去时,在处理容器内收纳形成有硼膜的基片,使处理容器内形成包含氧或者臭氧等的氧化气氛,利用电阻加热等对基片整体进行加热。
另外,对于在硼膜上形成微小图案的情况、除去基片的斜面(bevel)部或者端部的硼膜的情况等局部地进行除去的情况而言,在包含氧或者臭氧等的氧化气氛下对硼膜要除去的部分局部地进行加热。作为此情况下的加热方法,能够更适宜地使用激光或者灯(lamp)。
对于步骤1的通过热处理对硼膜进行氧化的方法,下面进行说明。
如上所述,对于通过CVD成膜得到的硼膜而言,作为成膜气体使用B2H6气体这样的包含硼和氢的气体,因此在膜中含有适当量的来自成膜气体的氢。对此状态下的硼膜即使像现有技术那样利用O2等离子体进行处理,氧也不会进入硼膜中而基本不会发生硼与氧的反应。
但是,当利用热处理对硼膜进行加热时,膜中含有的氢脱离。图2是表示CVD硼膜的升温脱离气体分析(TDS)的结果的图,可知温度上升从而H2气体逐渐脱离,在400℃附近氢的脱离量达到峰值。
然后,气氛中的氧侵入膜中的氢脱离的部分,通过加热与硼发生反应,成为氧化硼。图3是用于对O2热处理前后的硼膜的状态进行说明的SEM照片。热处理在O2气体气氛中、在800℃下进行了30分钟。如该图所示,可知处理前膜厚为140nm的硼膜通过O2热处理增厚到750nm,形成了氧化硼(BxOy)。此外,在硼膜中除氢以外还包含水分等其他成分,因此氧化后的膜厚比根据硼的氧化得到的计算上的膜厚要厚。
对此,O2等离子体处理(10min)的情况如图4的SEM照片所示,可知在处理前后硼膜未发生变化,没有形成氧化硼。
步骤1的热处理的温度优选在400℃以上。在低于400℃的温度下难以发生氢的脱离和硼的氧化。另外,对热处理的温度而言,从设备的观点看来优选为1000℃以下,从硼的热扩散的观点看来优选为800℃以下。
热处理时的氧化气氛的O2气体或者O3气体浓度优选为20~100%。除O2气体或者O3气体的部分之外能够使用氮气或者Ar气、He气这样的稀有气体等的不活泼气体。氧化气氛可以为空气。
热处理时间根据温度而不同,但优选在1~60min的程度。若不足1min则难以充分的发生氢的脱离和硼的氧化。另一方面,若超过60min则生产性变差。但是,如果要除去的硼膜的膜厚较厚,热处理温度较低,那么也存在需要60min以上的情况。
在进行了上面的热处理之后,通过利用水或者含有电解质离子(H+、NH4 +、F-、Cl-、NO3 -、SO4 2-、OH-等)的水溶液的进行处理除去经氧化的硼膜(步骤2)。由于氧化硼溶于水,因此通过利用水或者含有电解质离子的水溶液进行的处理能够除去氧化硼。作为含有电解质离子的水溶液,优选具有氧化性的酸以外的溶液。
关于该利用水或者含有电解质离子的水溶液进行的处理,可以将基片浸泡在纯水或者含有电解质离子的水溶液中,也可以利用纯水或者含有电解质离子的水溶液的水流来除去基片上的氧化硼。作为流水除去,能够使用这样的旋转处理,即通过旋转卡盘使基片旋转,同时向氧化硼供给纯水或者含有电解质离子的水溶液。另外,也可以进行供给水蒸气等的干处理。当浸泡于纯水或者含有电解质离子的水溶液时,可以利用超声波发生器对纯水施加超声波振动,来促进氧化硼的除去。利用水或者含有电解质离子的水溶液进行的处理的时间根据处理方法而不同,但是优选在1~30min的范围。
通过上面那样的包含步骤1和步骤2的方法,能够整体地或者局部地除去形成于基片上的硼膜。
如此,根据本实施方式,不使用等离子体处理(干法蚀刻(RIE)处理),通过热处理和水等的处理之类的简单的步骤就能够容易地除去硼膜。另外,由于不会如现有技术那样利用含有具有氧化能力的酸的药液来直接除去硼膜,而使硼膜局部地变为氧化硼,利用水等仅除去氧化硼的部分,因此能够局部地选择性地除去硼膜。
<对硼膜的图案形成的应用>
下面,对在硼膜的图案形成中应用了上述实施方式的硼膜除去方法的实施方式进行说明。
[第一例]
首先,说明对图案形成的应用的第一例。
图5是表示本例的图案形成方法的步骤截面图。
首先,准备在硅基片1上形成有绝缘膜2的晶片,在其上形成作为硬掩模的硼膜3(图5的(a))。
如上所述,硼膜3使用含有硼和氢的原料气体作为原料气体,通过CVD成膜而得。CVD可以为热CVD也可以为等离子体CVD,但是等离子体CVD更能够得到高密度且优良膜质的膜。对于等离子体CVD而言,温度优选为60~500℃(进一步优选为200~300℃),压力优选为0.67~33.3Pa。这样的CVD硼膜含有3.9~11.7at%左右的氢。
下面,对硼膜3而言,从氧喷嘴11供给O2气体或者O3气体以形成氧化气氛,并从作为热源的激光光源12与规定的微小图案对应地向局部地(部分)照射激光13,进行激光加热(热处理)(图5的(b))。由此在,被激光照射而局部地被加热的部分形成氧化硼4(图5的(c))。此时的热处理条件与上述的条件相同。
下面,利用水或者含有电解质离子的水溶液对形成有氧化硼4的晶片进行处理,以对氧化硼4进行溶解除去(图5的(d))。由此,形成硼膜的微小图案。此时的水等的处理也能够使用如上述那样向纯水等中的浸泡、旋转处理等的利用纯水等的水流的处理。
在本例中,由于局部地(部分)进行在氧化气氛下的激光加热来形成氧化硼,因此能够容易地形成硼膜的微小图案。另外,通过使用激光加热,能够省略光刻步骤,能够以较少的步骤形成硼膜的微小图案。
[第二例]
下面,说明对图案形成的应用的第二例。
图6是表示本例的图案形成方法的步骤截面图。
首先,准备在硅基片1上形成有绝缘膜2的晶片,在其上形成作为硬掩模的硼膜3,灵活使用光刻和蚀刻步骤,硼膜3上形成由抗蚀剂或者掩模材料(绝缘物、金属等)的膜5得到的图案(图6的(a))。硼膜与第一例同样,使用含有硼和氢的原料气体作为原料气体,通过CVD成膜而得。
下面,对硼膜3而言,从氧喷嘴11供给O2气体或者O3气体以形成氧化气氛,并且通过使用了作为热源的灯光源14的灯加热,对与硼膜3的图案对应的部分(露出部分)局部地(部分)进行热处理(图6的(b))。由此,在与硼膜3的图案对应的部分形成氧化硼4(图6的(c))。此时的热处理条件与上述的条件相同。
下面,利用水对形成有氧化硼4的晶片进行处理,对氧化硼4进行溶解除去(图6的(d))。由此,能够形成硼膜的微小图案。此时的水等的处理也能够使用如上述那样向纯水等中的浸泡、旋转处理等的利用纯水等的水流的处理。
在本例中,由于对与抗蚀剂图案对应的部分进行局部的、在氧化气氛下的灯加热以形成氧化硼,因此能够容易地形成硼膜的微小图案。
<晶片端部的硼膜的局部的除去>
下面,对晶片端部的硼膜的局部的除去进行说明。
为了在半导体元件的形成中进行微小加工,使用光刻进行图案形成,近年来,对随着图案的进一步微小化而进行的短波长化(ArF,λ=193nm)或者利用了光折射的液浸曝光而言,从粒子(particle)或者污染问题的观点看来,非常需要对晶片端部(边缘、斜面)的膜进行管理。
因此,本实施方式给出将上述实施方式的硼膜除去方法应用于晶片端部的硼膜的局部的除去的例子。
[第一例]
首先,说明对晶片端部的局部的除去的应用的第一例。
图7是表示本例的晶片端部的局部的除去的步骤截面图。
在此,在晶片21上,通过上述的CVD形成有作为硬掩模的硼膜23时,对该晶片21的与端部(边缘、斜面)对应的部分从氧喷嘴11供给O2气体或者O3气体以形成氧化气氛,并且从作为热源的激光光源12与规定的微小图案对应地局部照射激光13,进行激光加热(热处理)(图7的(a))。由此如上述那样形成氧化硼,之后,利用水的处理,能够除去端部(边缘、斜面)的硼膜23(图7的(b))。
在本例中,由于仅对端部局部进行在氧化气氛下的加热以形成氧化硼,因此能够容易地以高精度对晶片端部(边缘/斜面)的硼膜进行除去。另外,通过使用激光加热,能够省略光刻步骤,能够以较少的步骤除去端部的硼膜。
[第二例]
下面,说明对晶片端部的局部的除去的应用的第二例。
图8是表示本例的晶片端部的局部的除去的步骤截面图。
在此,在晶片21上,通过上述的CVD形成有作为硬掩模的硼膜23时,在该晶片21的与端部(边缘、斜面)对应的部分以外的部分形成抗蚀剂或者掩模材料(绝缘物、金属等)的膜25,从氧喷嘴11供给O2气体或者O3气体以形成氧化气氛并且通过使用了作为热源的灯光源14的灯加热进行热处理(图8的(a))。由此,如上述那样形成氧化硼,之后利用水的处理,对端部(边缘、斜面)的硼膜23进行除去(图8的(b))。
在本例中,由于仅对端部局部进行在氧化气氛下的加热以形成氧化硼,因此能够容易地以高精度对晶片端部(边缘、斜面)的硼膜进行除去。
<实验结果>
下面,对实验结果进行说明。
[实验1]
在此,准备在硅晶片上形成有厚度为140nm的硼膜的样本,该硼膜是使用乙硼烷(B2H6)气体作为成膜原料气体,在温度:300℃,压力:50mTorr(6.67Pa)的条件下通过等离子体CVD而形成的,将该样本在O2气体气氛800℃下进行了30min的热处理之后,在以超声波振动的纯水中浸泡30分钟来进行了硼膜除去处理。图9表示此情况的处理前和处理后的SEM照片。如该照片所示,确认了通过热处理和利用纯水处理进行的硼膜除去处理,能够完全除去硼膜。
为了进行比较,准备通过PVD在硅晶片上形成了厚度为117nm的硼膜的样本,对该样本进行了同样的硼除去处理。图10表示此情况的处理前和处理后的SEM照片。如该照片所示,可知对于PVD硼膜的情况,尽管在800℃这样的较高温度下进行了热处理,但是在纯水处理后才除去了少量硼膜。本发明人认为这是由于对于PVD而言,膜中的氢含量较少,通过热处理基本不形成氧化硼的缘故。
[实验2]
在此,与实验1同样,准备多个形成有硼膜的样本,所述硼膜在硅晶片上使用乙硼烷(B2H6)气体作为成膜原料气体,在温度:300℃,压力:50mTorr(6.67Pa)的条件下通过等离子体CVD形成,使温度变为400℃、500℃、600℃,在O2气体气氛下对该样本进行了30分的热处理之后,在以超声波振动的纯水中浸泡30分钟来进行了硼膜除去处理。图11表示在处理前和在各温度下进行了热处理的处理后的SEM照片。如该图所示,确认了对于热处理温度为500℃和600℃的样本,通过热处理和利用纯水处理进行的硼膜除去处理,能够完全除去硼膜。另外,对于热处理温度为400℃的样本,通过硼膜除去处理多少除去了一些硼膜,但是若要完全除去,需要更长时间的处理。
[实验3]
在此,与实验1相同,准备多个形成有硼膜的样本,上述硼膜在硅晶片上使用乙硼烷(B2H6)气体作为成膜原料气体,在温度:300℃,压力:50mTorr(6.67Pa)的条件下通过等离子体CVD形成,使温度变为400℃、600℃、800℃,使时间变为1min、10min、20min、30min,对该样本进行了在O2气体气氛下的热处理之后,在以超声波振动的纯水中浸泡30分钟来进行了硼膜除去处理。图12表示处理前和在各温度和各时间下进行了热处理的处理后的SEM照片。如该图所示,对于热处理温度为800℃的情况,处理时间为1min时硼膜基本被除去。另外,对于热处理温度的600℃的情况,处理时间为1min时硼膜的厚度从140nm减少到120nm,处理时间为10min时硼膜几乎被除去。另外,在热处理温度为400℃的情况下,与实验2相同,处理时间为30min时多少除去了一些硼膜,但是若要完全除去,则需要更长时间的处理。
<其他应用>
以上,本发明的实施的方式进行了说明,但是本发明不限于上述实施方式,在本发明的思想的范围内可以进行各种变形。
例如,在上述实施方式中,作为硼膜的用途给出了硬掩模的例子,但是不限于此,对薄膜用途而言也能够用于防扩散用的防护膜等的其他用途。
另外,对氧化气氛下的热处理例示了通过激光加热、灯加热、电阻加热来进行的例子,根据硼膜的除去方式和目的,能够采用各种方法和装置,加热方法和装置没有限制。
另外,在上述实施的方式中,在硼膜的图案形成过程中,给出了使用了激光加热和灯加热的例子,只要能够与规定的图案对应地对布局(一部分)在氧化气氛下进行加热就没有限制。
另外,在上述实施的方式中,给出了形成于晶片(硅晶片)上的绝缘膜上的硼膜的除去和图案形成的例子,但是不限于此,也能够应用于在各种物质的上形成的硼膜的除去和图案形成。
Claims (12)
1.一种对通过CVD形成于基片上的硼膜进行除去的硼膜的除去方法,其特征在于,包括:
在氧化气氛下利用激光加热对所述硼膜局部地进行热处理,使经过热处理的部分氧化的第一步骤;和
利用水或者含有电解质离子的水溶液对所述硼膜的被氧化的部分进行除去的第二步骤,
通过所述第一步骤和所述第二步骤,不进行光刻步骤而将所述硼膜局部地除去。
2.如权利要求1所述的硼膜的除去方法,其特征在于:
所述氧化气氛包含氧或者臭氧。
3.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述电解质离子包含H+、NH4 +、F-、Cl-、NO3 -、SO4 2-和OH-中的任一者。
4.如权利要求3所述的硼膜的除去方法,其特征在于:
所述电解质离子的水溶液不包含具有氧化性的酸。
5.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述硼膜是使用包含硼和氢的原料气体成膜而得到的。
6.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述硼膜是通过等离子体CVD成膜而得到的。
7.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述第一步骤中的热处理在400~1000℃的范围的温度下进行。
8.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述第一步骤中的热处理进行1~60分钟的时间。
9.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述第一步骤中的热处理在氧气或者臭氧气体的浓度为20~100%的气氛下进行。
10.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述第二步骤通过将所述基片浸泡在纯水或者含有电解质离子的水溶液中来进行。
11.如权利要求10所述的硼膜的除去方法,其特征在于:
对浸泡有所述基片的纯水或者含有电解质离子的水溶液施加超声波振动。
12.如权利要求1或2所述的硼膜的除去方法,其特征在于:
所述第二步骤通过对所述基片供给纯水或者含有电解质离子的水溶液的水流来进行。
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