CN110724935A - 成膜方法和半导体装置的制造方法 - Google Patents
成膜方法和半导体装置的制造方法 Download PDFInfo
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- CN110724935A CN110724935A CN201910644005.0A CN201910644005A CN110724935A CN 110724935 A CN110724935 A CN 110724935A CN 201910644005 A CN201910644005 A CN 201910644005A CN 110724935 A CN110724935 A CN 110724935A
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- oxide film
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- oxide
- gallium
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- 238000000034 method Methods 0.000 title claims abstract description 79
- 239000004065 semiconductor Substances 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000000758 substrate Substances 0.000 claims abstract description 97
- 239000003595 mist Substances 0.000 claims abstract description 77
- 239000000463 material Substances 0.000 claims abstract description 57
- -1 organogermanium compound Chemical class 0.000 claims abstract description 47
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 44
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 31
- 150000002259 gallium compounds Chemical class 0.000 claims description 21
- IQULGZQMMPRBLA-UHFFFAOYSA-N 2-carboxyethylgermanium Chemical compound OC(=O)CC[Ge] IQULGZQMMPRBLA-UHFFFAOYSA-N 0.000 claims description 19
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 14
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910003437 indium oxide Inorganic materials 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZVYYAYJIGYODSD-LNTINUHCSA-K (z)-4-bis[[(z)-4-oxopent-2-en-2-yl]oxy]gallanyloxypent-3-en-2-one Chemical compound [Ga+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O ZVYYAYJIGYODSD-LNTINUHCSA-K 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical group [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002472 indium compounds Chemical class 0.000 claims description 4
- 150000003752 zinc compounds Chemical class 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 54
- 239000012159 carrier gas Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 18
- 239000003085 diluting agent Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000002019 doping agent Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 6
- 229940093626 germanium sesquioxide Drugs 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910005222 Ga2Cl6 Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 229910052733 gallium Chemical group 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- SYWSGAXJMRGDKW-UHFFFAOYSA-N germanium;trimethylsilicon Chemical compound [Ge].C[Si](C)C.C[Si](C)C.C[Si](C)C SYWSGAXJMRGDKW-UHFFFAOYSA-N 0.000 description 1
- WHYHZFHCWGGCOP-UHFFFAOYSA-N germyl Chemical compound [GeH3] WHYHZFHCWGGCOP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- LRPWSMQGXLANTG-UHFFFAOYSA-M iodogallium Chemical compound I[Ga] LRPWSMQGXLANTG-UHFFFAOYSA-M 0.000 description 1
- XCLKKWIIZMHQIV-UHFFFAOYSA-N isobutylgermane Chemical compound CC(C)C[Ge] XCLKKWIIZMHQIV-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- CUDGTZJYMWAJFV-UHFFFAOYSA-N tetraiodogermane Chemical compound I[Ge](I)(I)I CUDGTZJYMWAJFV-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明涉及成膜方法和半导体装置的制造方法。提出适宜地形成由氧化物构成并具有导体或半导体的特性的氧化物膜的技术。提出在基板上形成掺杂有锗且具有导体或半导体的特性的氧化物膜的成膜方法。该成膜方法具有如下工序:一边加热上述基体,一边向上述基体的表面供给溶解有包含上述氧化物膜的构成元素的氧化物膜材料和有机锗化合物的溶液的雾。
Description
技术领域
本说明书中公开的技术涉及在基体上形成膜的技术。
背景技术
专利文献1公开了在基板的表面形成氧化物膜的技术。该技术中,一边加热基板,一边向基板的表面供给溶解有氧化物膜材料和掺杂剂材料的溶液的雾。根据该技术,可在基板的表面生长添加有锗作为掺杂剂的氧化物膜。
现有技术文献
专利文献
专利文献1:日本特开2015-070248号公报
发明内容
发明所要解决的课题
在专利文献1的技术中,作为掺杂剂材料,使用氧化锗、氯化锗、溴化锗、碘化锗等。在该成膜方法中,合适的成膜条件因掺杂剂的供给量而大幅变化,因此,难以准确地控制氧化物膜的导电性。因此,在本说明书中,提出了在形成具有导体或半导体的特性的氧化物膜时能更准确地控制氧化物膜的导电性的技术。
用于解决课题的手段
本说明书公开的成膜方法在基体上形成掺杂有锗并具有导体或半导体的特性的氧化物膜。该成膜方法具有如下工序:一边加热上述基体,一边向上述基体的表面供给溶解有包含上述氧化物膜的构成元素的氧化物膜材料和有机锗化合物的溶液的雾。
在该成膜方法中,使用有机锗化合物作为掺杂剂材料,形成添加有锗的氧化物膜。根据该成膜方法,能准确地控制氧化物膜的导电性。
附图说明
图1是成膜装置10的构成图。
附图标记说明
10:成膜装置
12:炉
13:基板台
14:加热器
20:雾供给装置
22:容器
24:超声波换能器
26:雾供给路
28:运载气体导入路
30:稀释气体导入路
60:溶液
62:雾
64:运载气体
66:稀释气体
70:基板
80:排出管
具体实施方式
实施例
图1所示的成膜装置10是在基板70上形成氧化物膜的装置。成膜装置10具备:配置基板70的炉12、对炉12进行加热的加热器14、与炉12连接的雾供给装置20和与炉12连接的排出管80。
对炉12的具体构成没有特别限定。作为一例,图1所示的炉12为从上游端12a至下游端12b延伸的管状炉。与炉12的纵向垂直的断面为圆形。例如,可将炉12的直径设为约40mm。不过,炉12的断面不限于圆形。炉12的上游端12a连接有雾供给装置20。炉12的下游端12b连接有排出管80。
炉12内设有用于支撑基板70的基板台13。基板台13以基板70相对于炉12的纵向倾斜的方式构成。支撑于基板台13的基板70在从上游端12a向下游端12b在炉12内流动的雾碰撞基板70的表面的朝向上被支撑。
如前所述,加热器14对炉12进行加热。对加热器14的具体构成没有特别限定。作为一例,图1所示的加热器14为电加热器且沿着炉12的外周壁配置。由此,加热器14对炉12的外周壁进行加热,从而炉12内的基板70被加热。
雾供给装置20向炉12内供给包含氧化物膜的原料的溶液的雾。对雾供给装置20的具体构成没有特别限定。作为一例,图1所示的雾供给装置20具备:收容溶液60的容器22、设于容器22的超声波换能器24、将容器22和炉12之间连接的雾供给路26、与容器22连接的运载气体导入路28、和与雾供给路26连接的稀释气体导入路30。运载气体导入路28向容器22供给运载气体64。稀释气体导入路30向雾供给路26供给稀释气体66。超声波换能器24对容器22内的溶液60施加超声波振动,生成溶液60的雾62。
排出管80与炉12的下游端12b连接。由雾供给装置20向炉12内供给的雾62在炉12内流动至下游端12b后,经由排出管80排出至炉12的外部。
实施例1
接着,对使用了成膜装置10的成膜方法进行说明。在实施例1中,作为基板70,使用由表面露出有(010)晶面的β型氧化镓(β-Ga2O3)的单晶构成的基板。另外,在实施例1中,在基板70的表面形成β型氧化镓膜。另外,在实施例1中,作为溶液60,使用溶解有氯化镓(GaCl3或Ga2Cl6)和β-羧基乙基锗倍半氧化物((GeCH2CH2COOH)2O3)的水溶液。氯化镓为氧化镓膜的原料。β-羧基乙基锗倍半氧化物是作为掺杂剂材料使用的有机锗化合物。即,在实施例1中,氧化物膜为β型氧化镓膜,氧化物膜材料为氯化镓,有机锗化合物为β-羧基乙基锗倍半氧化物。在溶液60中以0.5mol/L的浓度溶解有氯化镓,以1×10-4mol/L的浓度溶解有β-羧基乙基锗倍半氧化物。另外,在实施例1中,使用氮气作为运载气体64,使用氮气作为稀释气体66。
如图1所示那样,首先,在炉12内的基板台13上设置基板70。在此,在基板70的(010)晶面成为顶面(暴露于雾62的面)的朝向将基板70设置在基板台13上。接着,利用加热器14对基板70进行加热。在此,将基板70的温度控制为约750℃。基板70的温度稳定时,使雾供给装置20工作。即,通过使超声波换能器24工作,在容器22内生成溶液60的雾62。同时,从运载气体导入路28向容器22内导入运载气体64,从稀释气体导入路30向雾供给路26导入稀释气体66。在此,将运载气体64和稀释气体66的合计流量设为约5L/min。运载气体64通过容器22,如箭头44所示那样流入雾供给路26内。此时,容器22内的雾62与运载气体64一起流入雾供给路26内。另外,稀释气体66在雾供给路26内与雾62混合。由此,将雾62稀释。雾62与氮气(即,运载气体64和稀释气体66)一起在雾供给路26内流向下游侧,如箭头48所示那样从雾供给路26流入炉12内。在炉12内,雾62与氮气一起流向下游端12b侧,向排出管80排出。
在炉12内流动的雾62的一部分附着于加热了的基板70的表面。这样,雾62(即,溶液60)在基板70上引起化学反应。其结果,在基板70上生成β型氧化镓(β-Ga2O3)。由于向基板70的表面连续地供给雾62,因此β型氧化镓膜在基板70的表面生长。根据该成膜方法,高品质的单晶的β型氧化镓膜生长。β型氧化镓膜中纳入β-羧基乙基锗倍半氧化物中的锗原子作为供体。因此,形成掺杂有锗的β型氧化镓膜。在此,进行30分钟的成膜处理,消耗约50ml的溶液60,生长β型氧化镓膜。对通过该成膜方法形成的β型氧化镓膜的特性利用霍尔效应测定进行测定,结果,观测到6.5×1018cm-3的载流子密度和55cm2/Vsec的迁移率。
根据实施例1的成膜方法,可形成高品质的β型氧化镓膜。特别地,在实施例1中,由于β型氧化镓膜在由β型氧化镓构成的基板70上进行同质外延生长,因此,可形成更高品质的β型氧化镓膜。另外,由于使用有机锗化合物作为掺杂剂材料,因此可准确地控制β型氧化镓膜的导电性。特别地,由于是同质外延生长,因此可更准确地控制导电性。
实施例2
接着,对实施例2的成膜方法进行说明。在实施例2中,作为基板70,使用由蓝宝石(Al2O3)构成的基板。另外,在实施例2中,在基板70的表面形成α型氧化镓膜。另外,在实施例2中,作为溶液60,使用溶解有溴化镓(GaBr3、Ga2Br6)和β-羧基乙基锗倍半氧化物((GeCH2CH2COOH)2O3)的水溶液。溴化镓为氧化镓膜的原料。β-羧基乙基锗倍半氧化物为作为掺杂剂材料使用的有机锗化合物。即,在实施例2中,氧化物膜为α型氧化镓膜,氧化物膜材料为溴化镓,有机锗化合物为β-羧基乙基锗倍半氧化物。溶液60中以0.1mol/L的浓度溶解有溴化镓,以1×10-4mol/L的浓度溶解有β-羧基乙基锗倍半氧化物。另外,在实施例2中,使用氮气作为运载气体64,使用氮气作为稀释气体66。
在实施例2的成膜方法中,也与实施例1同样地,在基板台13上设置基板70,利用加热器14对基板70进行加热。在此,将基板70的温度控制为约500℃。基板70的温度稳定时,使雾供给装置20工作。即,与实施例1同样地实施超声波换能器24的工作、运载气体64的导入和稀释气体66的导入。其结果,雾62流入炉12内,在炉12内流动的雾62的一部分附着于加热了的基板70的表面。这样,雾62(即,溶液60)在基板70上引起化学反应。其结果,在基板70上生成α型氧化镓(α-Ga2O3)。由于向基板70的表面连续地供给雾62,因此α型氧化镓膜在基板70的表面生长。根据该成膜方法,高品质的单晶的α型氧化镓膜生长。α型氧化镓膜中纳入β-羧基乙基锗倍半氧化物中的锗原子作为供体。因此,形成掺杂有锗的α型氧化镓膜。根据实施例2的成膜方法,由于使用有机锗化合物作为掺杂剂材料,因此,可准确地控制α型氧化镓膜的导电性。
实施例3
接着,对实施例3的成膜方法进行说明。在实施例3中,作为基板70,使用由玻璃构成的基板。另外,在实施例3中,在基板70的表面形成氧化锌膜(ZnO)。另外,在实施例3中,作为溶液60,使用溶解有乙酸锌(Zn(Ac2)2,其中,Ac表示乙酰基)和β-羧基乙基锗倍半氧化物((GeCH2CH2COOH)2O3)的水溶液。乙酸锌为氧化锌膜的原料。β-羧基乙基锗倍半氧化物为作为掺杂剂材料使用的有机锗化合物。即,在实施例3中,氧化物膜为氧化锌膜,氧化物膜材料为乙酸锌,有机锗化合物为β-羧基乙基锗倍半氧化物。溶液60中以0.05mol/L的浓度溶解有乙酸锌,以1×10-4mol/L的浓度溶解有β-羧基乙基锗倍半氧化物。另外,在实施例3中,使用氮气作为运载气体64,使用氮气作为稀释气体66。
在实施例3的成膜方法中,也与实施例1同样地,在基板台13上设置基板70。接着,利用加热器14对基板70进行加热。在此,将基板70的温度控制为约400℃。基板70的温度稳定时,使雾供给装置20工作。即,与实施例1同样地实施超声波换能器24的工作、运载气体64的导入和稀释气体66的导入。其结果,雾62流入炉12内,在炉12内流动的雾62的一部分附着于加热了的基板70的表面。这样,雾62(即,溶液60)在基板70上引起化学反应。其结果,在基板70上生成氧化锌(ZnO)。由于向基板70的表面连续地供给雾62,因此氧化锌膜在基板70的表面生长。根据该成膜方法,高品质的单晶的氧化锌膜生长。氧化锌膜中纳入β-羧基乙基锗倍半氧化物中的锗原子作为供体。因此,形成掺杂有锗的氧化锌膜。根据实施例3的成膜方法,由于使用有机锗化合物作为掺杂剂材料,因此,可准确地控制氧化锌膜的导电性。
如在以上的实施例1~3中所说明的那样,通过使用溶解有包含氧化物膜的构成元素的氧化物膜材料和有机锗化合物的溶液的雾来使氧化物膜生长,可形成掺杂有锗的氧化物膜。予以说明,在使用锡(Sn)作为供体的情况下,锡可取得二价和四价的氧化数,而作为供体发挥功能的仅为四价的锡,因此,不能准确地控制氧化物膜的导电性。另外,虽然也可以在溶解有锡的溶液中添加盐酸和/或过氧化氢溶液而使锡成为四价,但是,在溶液中添加盐酸和/或过氧化氢溶液时,氧化物膜的生长速度变慢。与此相对,在如实施例1~3那样使用锗作为供体时,即使在锗的溶液中不添加盐酸和/或过氧化氢溶液,也可比较准确地控制氧化物膜的导电性。特别地,通过使用有机锗化合物作为掺杂剂材料,能更准确地控制氧化物膜的导电性。因此,根据实施例1~3的成膜方法,能准确地控制氧化物膜的导电性并以快的成膜速度使氧化物膜生长。通过使用如实施例1~3那样地成膜的氧化物膜制造半导体装置(例如二极管、晶体管等),可得到具有优异特性的半导体装置。
另外,在上述实施例1、2中,均是在溶液60中溶解的锗原子的数量(浓度)为在溶液60中溶解的镓原子的数量(浓度)的10倍以下。根据该构成,可形成晶体品质高的氧化镓膜。另外,在上述实施例3中,在溶液60中溶解的锗原子的数量(浓度)为在溶液60中溶解的锌原子的数量(浓度)的10倍以下。根据该构成,可形成晶体品质高的氧化锌膜。
另外,在上述实施例1~3中,将基板70加热至400~750℃。在成膜工序中,可将基板70控制为400~1000℃的温度。通过这样控制温度,可更合适地形成氧化镓膜、氧化锌膜。
予以说明,在实施例1~3中,在基板70的表面形成了氧化镓膜(Ga2O3)或氧化锌膜(ZnO)。不过,也可以在基板70的表面形成其它氧化物膜。例如,可以形成氧化铟膜(In2O3)或氧化铝膜(Al2O3)。另外,也可以形成组合了氧化铟、氧化铝和氧化镓的材料(即,InxAlyGazO3(0≤x≤2,0≤y≤2,0≤z≤2))的膜。在形成氧化铟膜的情况下,作为溶解在溶液60中的氧化物膜材料,可使用铟化合物。在形成氧化铝膜的情况下,作为溶解在溶液60中的氧化物膜材料,可使用铝化合物。在形成组合了氧化铟、氧化铝和氧化镓的材料的膜的情况下,作为溶解在溶液60中的氧化物膜材料,可组合地使用铟化合物、铝化合物和镓化合物。这些情况下,通过使雾62中包含的锗原子的数量(即,摩尔浓度)为雾62中包含的铟原子、铝原子和镓原子的总数(即,铟原子、铝原子和镓原子的摩尔浓度的合计值)的10倍以下,可形成结晶性高的氧化物膜。
另外,在上述实施例1~3中,形成了单晶的氧化物膜。但是,也可以形成无定形或多晶的氧化物膜。
另外,在上述实施例1~3中,基板70由β型氧化镓、蓝宝石或玻璃构成。不过,基板70也可以由其它材料构成。通过使用由其它材料构成的基板70,可形成与实施例1~3不同特性的氧化物膜。例如,基板70可由α型氧化镓(α-Ga2O3)、γ型氧化镓、δ型氧化镓、ε型氧化镓、氧化铝(例如α型氧化铝(α-Al2O3))或氮化镓(GaN)等构成。另外,基板70可以为绝缘体,可以为半导体,也可以为导体。
另外,在上述实施例1~3中,基板70(即,板状的部件)的表面形成了氧化物膜。不过,可以使用其它形状的部件作为基材并在该基材的表面形成氧化物膜。
另外,在上述实施例1~3中,在溶液60中溶解的有机锗化合物为β-羧基乙基锗倍半氧化物。不过,可以使用其它材料作为在溶液60中溶解的有机锗化合物。予以说明,为了形成高品质的氧化镓膜,有机锗化合物可以为金属络合物。例如,作为有机锗化合物,可使用异丁基锗烷((Me2CHCH2)GeH3:其中,Me表示甲基)、三(三甲基甲硅烷基)锗氢化物((Me2Si)3GeH:其中,Me表示甲基)、丙帕锗(C6H10O7Ge2)等。不过,β-羧基乙基锗倍半氧化物由于便宜且安全性高,因此更容易使用。
另外,在上述实施例1、2中,在溶液60中溶解的镓化合物为氯化镓或溴化镓。不过,可以使用其它材料作为在溶液60中溶解的镓化合物。予以说明,为了形成高品质的氧化镓膜,镓化合物可以为有机物。另外,镓化合物可以为金属络合物。或者,镓化合物可以为卤化物。例如,作为镓化合物,可使用乙酰丙酮镓(例如镓(III)乙酰丙酮(C15H21GaO6))、三乙酸镓(C6H9GaO6)、碘化镓(GaI3、Ga2I6)等。不过,氯化镓(特别是氯化镓(III))由于便宜且可形成残留杂质少的膜,因此更容易使用。
另外,在上述实施例3中,在溶液60中溶解的锌化合物为乙酸锌。不过,可以使用其它材料作为在溶液60中溶解的锌化合物。
另外,在实施例1~3中,容器22收容溶解有氧化物膜材料和有机锗化合物这两者的溶液60,从该溶液60生成雾,将生成的雾供给至炉12。不过,可以各自单独地设置第1容器(其收容溶解有氧化物膜的溶液)和第2容器(其收容溶解有有机锗化合物的溶液)。然后,可以在第1容器内生成溶解有氧化物膜材料的溶液的第1雾,在第2容器内生成溶解有有机锗化合物的溶液的第2雾,将第1雾和第2雾供给至炉12。
另外,在实施例1~3中,使用了氮作为运载气体64和稀释气体66,但可使用非活性气体等其它气体作为运载气体64和稀释气体66。
关于本说明书公开的技术要素,在以下列出。予以说明,以下的各技术要素各自独立地是有用的。
在本说明书公开的一例的成膜方法中,向基体的表面供给溶解有氧化物膜材料和有机锗化合物的溶液的雾的工序可具有:从溶解有上述氧化物膜材料和上述有机锗化合物这两者的溶液生成雾的工序,和向上述基体的上述表面供给溶解有上述氧化物膜材料和上述有机锗化合物这两者的上述溶液的上述雾的工序。
在本说明书公开的另一例的成膜方法中,向基体的表面供给溶解有氧化物膜材料和有机锗化合物的溶液的雾的工序可具有:从溶解有上述氧化物膜材料的溶液生成雾的工序,从溶解有上述有机锗化合物的溶液生成雾的工序,和向上述基体的上述表面供给溶解有上述氧化物膜材料的上述溶液的上述雾和溶解有上述有机锗化合物的上述溶液的上述雾的工序。
因此,用从溶解有氧化物膜材料和有机锗化合物这两者的溶液生成雾的方法以及将溶解有氧化物膜材料的溶液和溶解有有机锗化合物的溶液分别进行雾化的方法中的任一者都能适宜地形成氧化物膜。
在本说明书公开的一例的成膜方法中,氧化物膜可以为单晶膜。
通过形成单晶的氧化物膜,可将氧化物膜合适地用于半导体元件等。
在本说明书公开的一例的成膜方法中,有机锗化合物可以为金属络合物。
在本说明书公开的一例的成膜方法中,有机锗化合物可以为β-羧基乙基锗倍半氧化物。
在本说明书公开的一例的成膜方法中,氧化物膜可以由氧化铟、氧化铝、氧化镓或将它们组合而成的氧化物构成。该情况下,氧化物膜材料可以包含铟化合物、铝化合物和镓化合物中的至少一种。
在本说明书公开的一例的成膜方法中,氧化物膜可以由氧化锌构成。该情况下,氧化物膜材料可包含锌化合物。
在本说明书公开的一例的成膜方法中,氧化物膜可以由氧化镓或包含氧化镓的氧化物构成。该情况下,氧化物膜材料可以为镓化合物。
在本说明书公开的一例的成膜方法中,上述镓化合物可以为有机物。
在本说明书公开的一例的成膜方法中,上述镓化合物可以为金属络合物。
在本说明书公开的一例的成膜方法中,上述镓化合物可以为乙酰丙酮镓。
在本说明书公开的一例的成膜方法中,上述镓化合物可以为卤化物。
在本说明书公开的一例的成膜方法中,上述镓化合物可以为氯化镓。
氯化镓便宜并且难以生成残留杂质。因此,作为氧化物膜材料是有用的。
在本说明书公开的一例的成膜方法中,溶解有氧化物膜材料和有机锗化合物的溶液的雾中包含的锗原子的数量为溶解有氧化物膜材料和有机锗化合物的溶液的雾中包含的铟原子、铝原子和镓原子的总数的10倍以下。
根据该构成,可形成晶体品质高的氧化物膜。
在本说明书公开的一例的成膜方法中,基体可以由氧化镓构成。
在本说明书公开的一例的成膜方法中,基体可以由β-Ga2O3构成。
在本说明书公开的一例的成膜方法中,基体可以由α-Ga2O3构成。
在本说明书公开的一例的成膜方法中,基体可以由α-Al2O3构成。
在本说明书公开的一例的成膜方法中,氧化物膜可以由β-Ga2O3构成。
根据该构成,氧化物膜的特性稳定,容易控制氧化物膜的导电性。
在本说明书公开的一例的成膜方法中,在形成上述氧化物膜时,可将上述基体加热至400~1000℃。
根据该构成,可形成晶体品质高的氧化物膜,并可准确地控制氧化物膜的导电性。
以上,对实施方式进行了详细说明,但这些仅为例示,不限定专利权利要求书。专利权利要求书中记载的技术包含将以上例示的具体例进行各种变形、改变而得的例子。本说明书或附图中说明的技术要素通过单独或各种组合来发挥技术有用性,不限定于申请时权利要求书中记载的组合。另外,本说明书或附图中例示的技术同时实现多个目的,实现其中的一个目的自身具有技术有用性。
Claims (22)
1.成膜方法,其是在基体上形成掺杂有锗并具有导体或半导体的特性的氧化物膜的成膜方法,其具有如下工序:
一边加热上述基体,一边向上述基体的表面供给溶解有包含上述氧化物膜的构成元素的氧化物膜材料和有机锗化合物的溶液的雾。
2.权利要求1所述的成膜方法,其中,向上述基体的上述表面供给溶解有上述氧化物膜材料和上述有机锗化合物的溶液的雾的上述工序具有:
从溶解有上述氧化物膜材料和上述有机锗化合物这两者的溶液生成雾的工序,和
向上述基体的上述表面供给溶解有上述氧化物膜材料和上述有机锗化合物这两者的上述溶液的上述雾的工序。
3.权利要求1所述的成膜方法,其中,向上述基体的上述表面供给溶解有上述氧化物膜材料和上述有机锗化合物的溶液的雾的上述工序具有:
从溶解有上述氧化物膜材料的溶液生成雾的工序,
从溶解有上述有机锗化合物的溶液生成雾的工序,和
向上述基体的上述表面供给溶解有上述氧化物膜材料的上述溶液的上述雾和溶解有上述有机锗化合物的上述溶液的上述雾的工序。
4.权利要求1~3的任一项所述的成膜方法,其中,上述氧化物膜为单晶膜。
5.权利要求1~4的任一项所述的成膜方法,其中,上述有机锗化合物为金属络合物。
6.权利要求1~5的任一项所述的成膜方法,其中,上述有机锗化合物为β-羧基乙基锗倍半氧化物。
7.权利要求1~6的任一项所述的成膜方法,其中,上述氧化物膜由氧化铟、氧化铝、氧化镓或将它们组合而成的氧化物构成,
上述氧化物膜材料包含铟化合物、铝化合物和镓化合物中的至少一种。
8.权利要求1~6的任一项所述的成膜方法,其中,上述氧化物膜由氧化锌构成,
上述氧化物膜材料包含锌化合物。
9.权利要求1~6的任一项所述的成膜方法,其中,上述氧化物膜由氧化镓或包含氧化镓的氧化物构成,
上述氧化物膜材料为镓化合物。
10.权利要求9所述的成膜方法,其中,上述镓化合物为有机物。
11.权利要求9或10所述的成膜方法,其中,上述镓化合物为金属络合物。
12.权利要求9~11的任一项所述的成膜方法,其中,上述镓化合物为乙酰丙酮镓。
13.权利要求9所述的成膜方法,其中,上述镓化合物为卤化物。
14.权利要求9或13所述的成膜方法,其中,上述镓化合物为氯化镓。
15.权利要求1~14的任一项所述的成膜方法,其中,溶解有上述氧化物膜材料和上述有机锗化合物的上述溶液的上述雾中包含的锗原子的数量为溶解有上述氧化物膜材料和上述有机锗化合物的上述溶液的上述雾中包含的铟原子、铝原子和镓原子的总数的10倍以下。
16.权利要求1~15的任一项所述的成膜方法,其中,上述基体由氧化镓构成。
17.权利要求16所述的成膜方法,其中,上述基体由β-Ga2O3构成。
18.权利要求16所述的成膜方法,其中,上述基体由α-Ga2O3构成。
19.权利要求1~15的任一项所述的成膜方法,其中,上述基体由α-Al2O3构成。
20.权利要求1~7、9~19的任一项所述的成膜方法,其中,上述氧化物膜由β-Ga2O3构成。
21.权利要求1~20的任一项所述的成膜方法,其中,在形成上述氧化物膜时,将上述基体加热至400~1000℃。
22.制造方法,其为半导体装置的制造方法,其具备如下工序:利用权利要求1~21的任一项所述的成膜方法形成上述氧化物膜。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200620424A (en) * | 2004-08-25 | 2006-06-16 | Showa Denko Kk | Germanium-adding source for compound semiconductor, production method of compound semiconductor using the same and compound semiconductor |
JP2015070248A (ja) * | 2013-10-01 | 2015-04-13 | 株式会社Flosfia | 酸化物薄膜及びその製造方法 |
CN105097957A (zh) * | 2014-05-08 | 2015-11-25 | Flosfia株式会社 | 结晶性层叠结构体、半导体装置 |
CN105986246A (zh) * | 2015-01-29 | 2016-10-05 | Flosfia株式会社 | 成膜装置和成膜方法 |
JP2016201555A (ja) * | 2015-04-10 | 2016-12-01 | 株式会社Flosfia | 結晶性酸化物半導体膜および半導体装置 |
CN107799584A (zh) * | 2016-08-31 | 2018-03-13 | 流慧株式会社 | 结晶性氧化物半导体膜、半导体装置及半导体系统 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5767588A (en) * | 1980-10-13 | 1982-04-24 | Tokyo Denshi Zairyo Kogyo Kk | Preparation of beta-carboxyethyl germanium sesquioxide |
US5725912A (en) * | 1993-11-22 | 1998-03-10 | Lin; Pan-Tien | Method of manufacturing an electric heating film of semiconductor |
JPH07257945A (ja) * | 1994-03-18 | 1995-10-09 | Nippon Soda Co Ltd | 透明導電性積層体及びペン入力タッチパネル |
JP2003205235A (ja) * | 2002-01-16 | 2003-07-22 | Canon Inc | 傾斜膜の製造方法および装置 |
JP2005200737A (ja) * | 2004-01-19 | 2005-07-28 | Konica Minolta Holdings Inc | 透明導電膜形成方法 |
US7223441B2 (en) * | 2004-03-10 | 2007-05-29 | Pilkington North America, Inc. | Method for depositing gallium oxide coatings on flat glass |
JP4742584B2 (ja) * | 2004-03-23 | 2011-08-10 | 株式会社豊田中央研究所 | 電極 |
JP2008078113A (ja) * | 2006-08-25 | 2008-04-03 | Fujikura Ltd | 透明導電性基板の製造装置 |
JPWO2012105229A1 (ja) * | 2011-02-02 | 2014-07-03 | 株式会社クラレ | 耐湿熱膜とその製造方法、デバイス、及び太陽電池 |
JP2013020942A (ja) * | 2011-04-28 | 2013-01-31 | Sumitomo Metal Mining Co Ltd | 有機el用透明導電性基材の製造方法、およびそれを用いた有機el用透明導電性基材、並びに有機el素子 |
JP2013105722A (ja) * | 2011-11-16 | 2013-05-30 | Kuraray Co Ltd | 透光性導電膜とその製造方法、デバイス、及び太陽電池 |
JP6137668B2 (ja) * | 2012-08-26 | 2017-05-31 | 国立大学法人 熊本大学 | 酸化亜鉛結晶層の製造方法及びミスト化学気相成長装置 |
US10109707B2 (en) * | 2014-03-31 | 2018-10-23 | Flosfia Inc. | Crystalline multilayer oxide thin films structure in semiconductor device |
JP6539906B2 (ja) * | 2014-09-25 | 2019-07-10 | 株式会社Flosfia | 結晶性積層構造体の製造方法および半導体装置 |
JP2017095743A (ja) * | 2015-11-19 | 2017-06-01 | 日本曹達株式会社 | Ito導電膜の成膜方法 |
JP6793942B2 (ja) * | 2016-11-01 | 2020-12-02 | 国立大学法人 和歌山大学 | 酸化ガリウムの製造方法及び結晶成長装置 |
KR20190074288A (ko) * | 2016-11-07 | 2019-06-27 | 가부시키가이샤 플로스피아 | 결정성 산화물 반도체막 및 반도체 장치 |
JP6831264B2 (ja) | 2017-02-23 | 2021-02-17 | テルモ株式会社 | 医療デバイス |
-
2018
- 2018-07-17 JP JP2018134344A patent/JP2020011858A/ja active Pending
-
2019
- 2019-07-16 KR KR1020190085721A patent/KR20200008966A/ko not_active Application Discontinuation
- 2019-07-16 DE DE102019119200.5A patent/DE102019119200A1/de not_active Ceased
- 2019-07-16 US US16/512,442 patent/US20200027730A1/en not_active Abandoned
- 2019-07-17 CN CN201910644005.0A patent/CN110724935A/zh active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW200620424A (en) * | 2004-08-25 | 2006-06-16 | Showa Denko Kk | Germanium-adding source for compound semiconductor, production method of compound semiconductor using the same and compound semiconductor |
JP2015070248A (ja) * | 2013-10-01 | 2015-04-13 | 株式会社Flosfia | 酸化物薄膜及びその製造方法 |
CN105097957A (zh) * | 2014-05-08 | 2015-11-25 | Flosfia株式会社 | 结晶性层叠结构体、半导体装置 |
CN105986246A (zh) * | 2015-01-29 | 2016-10-05 | Flosfia株式会社 | 成膜装置和成膜方法 |
JP2016201555A (ja) * | 2015-04-10 | 2016-12-01 | 株式会社Flosfia | 結晶性酸化物半導体膜および半導体装置 |
CN107799584A (zh) * | 2016-08-31 | 2018-03-13 | 流慧株式会社 | 结晶性氧化物半导体膜、半导体装置及半导体系统 |
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