CN103866265B - 基于氮的双受主共掺氧化锌薄膜的制备方法 - Google Patents
基于氮的双受主共掺氧化锌薄膜的制备方法 Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 34
- 230000008021 deposition Effects 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 29
- 239000000370 acceptor Substances 0.000 claims description 28
- 229960001296 zinc oxide Drugs 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 11
- 238000010926 purge Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- -1 zinc Alkyl compound Chemical class 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910007542 Zn OH Inorganic materials 0.000 claims description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000070 arsenic hydride Inorganic materials 0.000 claims description 2
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical compound [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 claims description 2
- KRDDXSIKPQVLDP-UHFFFAOYSA-N methylarsenic Chemical compound [As]C KRDDXSIKPQVLDP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007348 radical reaction Methods 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- JRPGMCRJPQJYPE-UHFFFAOYSA-N zinc;carbanide Chemical compound [CH3-].[CH3-].[Zn+2] JRPGMCRJPQJYPE-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 10
- 230000012010 growth Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910006389 Li—N Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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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
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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Abstract
本发明公开基于氮的双受主共掺氧化锌薄膜的制备方法,其包括:将基片放入原子层沉积设备的反应腔室中;进行多组分的复合沉积;所述复合沉积包括在锌源沉积之前引入一次As掺杂源的沉积和氧源沉积之前引入一次氮掺杂源的沉积;循环沉积该多组分复合体,得到原子层沉积制备的N‑As的双受主共掺的氧化锌薄膜。本发明提供的基于氮的双受主共掺氧化锌薄膜的制备方法,利用ALD技术,在氧化锌薄膜生长的过程中,完成整个薄膜结构的共掺,得到N‑As双受主的共掺。本发明制备工艺简单,沉积和掺杂过程易于控制,制备所得共掺氧化锌薄膜有利于氧化锌薄膜的p型掺杂和提高p型电学性质的稳定性。
Description
技术领域
本发明涉及氧化锌薄膜的制备与掺杂技术领域,具体涉及一种基于氮的双受主共掺氧化锌薄膜的制备方法。
背景技术
氧化锌(ZnO)作为一种新型的II-Ⅵ族直接带隙宽禁带化合物,具有大的室温禁带宽度3.37eV,而且自由激子结合能高达60meV,作为半导体材料越来越受到人们的重视。与其它宽禁带半导体材料相比,ZnO薄膜生长温度低,抗辐射性好,受激辐射有较低的阈值功率和很高的能量转换效率,这些优点使ZnO正成为光电子、微电子、信息等高新技术的关键基础材料。然而本征ZnO由于存在缺陷,使得ZnO呈n型,p型ZnO薄膜制备是目前ZnO相关研究的热点和难点。氮掺杂虽然在理论上的计算使得p型ZnO的制备成为可能,但是众多实验表明,可能是由于掺入的N原子会结合形成N分子,占据置换位置((N2)o),形成一种双施主缺陷,导致单独N掺杂ZnO薄膜的不稳定性。为了解决该问题,目前共掺被认为是制备出相对稳定的p-ZnO薄膜最有发展前景的方向之一。
为了提高p型ZnO薄膜的稳定性,人们对双受主共掺杂技术进行了研究,主要包括Li-N、N-As和N-P双受主掺杂技术。2005年,Krtschil等人利用MOVPE技术制备出了N-As双受主共掺杂ZnO薄膜,研究发现单独N或As掺杂的ZnO薄膜并非整个样品都具有p型导电性能,即掺杂特性很不均匀,这是单独受主掺杂p型ZnO不稳定性的根源;与此相对,对于N-As双受主掺杂的ZnO薄膜而言,几乎整个薄膜都是p型导电,n型导电的区域几乎不存在了,因而p型ZnO的可重复性和稳定性都有了大幅度提高。据报道,N-As双受主掺杂ZnO薄膜的p型导电性能可以稳定存在几个月之久,参见:Krtschil等,Appl.Phys.Lett.,87,262105,2005。2007年,Vlasenflin等人[30]利用超声喷雾热分解技术制备出N-P双受主掺杂的ZnO薄膜。研究者认为,在N-P双受主掺杂ZnO中,形成PZn-2VZn。复合体受主,并可能进一步形成No-PZn-2VZn的双受主复合体,参见:Vlasenflin等,Solid StateCommunications,142,292–294,2007。
原子层沉积技术(ALD)对薄膜的成分和厚度具有出色地控制能力,所制备的薄膜保形性好、纯度高且均匀性好,被广泛的应用于制取高质量的薄膜材料,并得到了迅速发展,成为一种既有技术上的优势,又有市场潜力的薄膜制备技术。因此,扩展ALD技术的应用范围,寻求采用ALD技术的双受主共掺技术,对于p型ZnO薄膜的制备具有不可估量的科学和应用价值。
发明内容
本发明所要解决的技术问题是提供一种可以将As与N元素共同掺杂在氧化锌薄膜中的基于氮的双受主共掺氧化锌薄膜的制备方法。
为解决上述技术问题,本发明提供了一种基于氮的双受主共掺氧化锌薄膜的制备方法,包括:
将基片放入原子层沉积设备的反应腔室中;进行多组分的复合沉积;
所述复合沉积包括在锌源沉积之前引入一次As掺杂源的沉积和氧源沉积之前引入一次氮掺杂源的沉积;循环沉积该多组分复合体,得到原子层沉积制备的N-As的双受主共掺的氧化锌薄膜。
进一步地,所述基片是经过浓硫酸和双氧水处理,并经超纯水超声过的硅片、蓝宝石或玻璃,衬底表面带有羟基。
进一步地,所述As掺杂源的沉积顺序是指在Zn源沉积之前、与Zn同时通入腔室进行沉积或先Zn源沉积之后沉积As掺杂源。
进一步地,所述复合沉积包括在真空环境下依次用As掺杂源、锌源、氮掺杂源和氧源进行沉积得到N-As双受主共掺的ZnO薄膜。
进一步地,所述As掺杂源、锌源、氮掺杂源和氧源在沉积室内暴露时间依次为0.08s、0.075s、5s、0.08s、50s,基片衬底温度为300℃。
进一步地,在每次沉积之后采用高纯氮气清洗沉积室。
进一步地,所述锌源是含锌的烷基化合物或含锌的卤化物,所述氧源是水蒸汽或氧气等离子体;所述氮掺杂源为N2O、N2、NO、NO2或NH3等离子体,所述As掺杂源是含As的烷基化物、含As的氢化物或含As的卤化物。
进一步地,所述含锌的卤化物是氯化锌ZnCl2,所述含锌的烷基化合物是二乙基锌Zn(C2H5)2或二甲基锌Zn(CH3)2,所述含As的烷基化物是甲基砷As(CH3)3或三乙基砷As(CH2CH3)3,所述含As的氢化物是氢化砷AsH3。
进一步地,该制备方法还包括通过控制所述的氮掺杂源与水的通气时间来调节掺杂氧化锌薄膜中氮掺杂源与氧的比例;通过控制As掺杂源与锌源的通气时间来调节掺杂氧化锌薄膜中As掺杂与锌的比例。
本发明提供的基于氮的双受主共掺氧化锌薄膜的制备方法,利用ALD技术,在氧化锌薄膜生长的过程中,完成整个薄膜结构的共掺,得到N-As双受主的共掺。本发明制备工艺简单,沉积和掺杂过程易于控制,制备所得共掺氧化锌薄膜有利于氧化锌薄膜的p型掺杂和提高p型电学性质的稳定性。
附图说明
图1为本发明实施例提供的基于氮的双受主共掺氧化锌薄膜的制备方法流程示意图。
具体实施方式
参见图1,本发明实施例提供的一种基于氮的双受主共掺氧化锌薄膜的制备方法包括:
将硅衬底或者玻璃衬底用浓硫酸双氧水进行处理,再用超纯水超声波进行清洗,N2吹干,其中浓硫酸:双氧水=4:1,使得衬底表面带有羟基(-OH)。
抽真空并对衬底、腔室和管道进行加热,达到实验所需各种工作环境,其中衬底温度为300℃。
向ALD设备反应腔室中通入一种V族掺杂源者As(CH3)3,该掺杂源作为受主掺杂源沉积在衬底表面,之后采用N2载气吹扫反应腔室;其中掺杂源的通入时间为0.08s,N2的吹扫时间为50s。
向反应腔室中通入锌源Zn(C2H5)2,衬底表面未与As掺杂源反应的基团与锌源反应形成锌氧键;采用载气吹扫反应腔室;其中掺杂源的通入时间为0.075s,N2的吹扫时间为50s。
启动射频等离子体,向反应腔室中通入N2等离子体,作为另一受主掺杂源N,采用N2载气吹扫反应腔室;其中等离子体的通入时间为5s,放电功率为50W,放电时间为10s,载气N2的吹扫时间为50s。
向反应腔室中通入水作为氧源,水与未被N2等离子体反应的-Zn-C2H5基团发生反应形成Zn-OH键,与-As-CH3基团反应形成As-OH;其中水的通入时间为0.08s,N2的吹扫时间为50s。
重复上述循环沉积N-As共掺的ZnO薄膜。
本发明通过ALD逐层循环的生长方式生长N-As双受主的共掺的氧化锌薄膜,其中As在ZnO中替锌的位置(VZn),N替代O的位置,在薄膜中形成一定的复合体,双受主的共掺有利于对p型ZnO的可重复性和稳定性都有大幅度的提高。
最后所应说明的是,以上具体实施方式仅用以说明本发明的技术方案而非限制,尽管参照实例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的精神和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (4)
1.一种基于氮的双受主共掺氧化锌薄膜的制备方法,其特征在于,包括:
将基片放入原子层沉积设备的反应腔室中;
进行多组分的复合沉积;
所述复合沉积包括在锌源沉积之前引入一次As掺杂源的沉积和氧源沉积之前引入一次氮掺杂源的沉积;循环沉积该多组分复合体,得到原子层沉积制备的N-As的双受主共掺的氧化锌薄膜;所述基片是经过浓硫酸和双氧水处理,并经超纯水超声过的硅片、蓝宝石或玻璃,衬底表面带有羟基;
所述As掺杂源的沉积顺序是指在Zn源沉积之前、与Zn同时通入腔室进行沉积或先Zn源沉积之后沉积As掺杂源;所述复合沉积包括:
在真空环境下依次用As掺杂源、锌源、氮掺杂源和氧源进行沉积得到N-As双受主共掺的ZnO薄膜;所述氧源为水,水与未被N2等离子体反应的-Zn-C2H5基团发生反应形成Zn-OH键,与-As-CH3基团反应形成As-OH;所述As掺杂源、锌源、氮掺杂源和氧源在沉积室内暴露时间依次为0.08s、0.075s、5s、0.08s,基片衬底温度为300℃;在每次沉积之后采用高纯氮气清洗沉积室,N2的吹扫时间为50s。
2.根据权利要求1所述的制备方法,其特征在于,所述锌源是含锌的烷基化合物或含锌的卤化物,所述氧源是水蒸汽或氧气等离子体;所述氮掺杂源为N2O、N2、NO、NO2或NH3等离子体,所述As掺杂源是含As的烷基化物、含As的氢化物或含As的卤化物。
3.根据权利要求2所述的制备方法,其特征在于,所述含锌的卤化物是氯化锌ZnCl2,所述含锌的烷基化合物是二乙基锌Zn(C2H5)2或二甲基锌Zn(CH3)2,所述含As的烷基化物是甲基砷As(CH3)3或三乙基砷As(CH2CH3)3,所述含As的氢化物是氢化砷AsH3。
4.根据权利要求2所述的制备方法,其特征在于,还包括:
通过控制所述的氮掺杂源与水的通气时间来调节掺杂氧化锌薄膜中氮掺杂源与氧的比例;通过控制As掺杂源与锌源的通气时间来调节掺杂氧化锌薄膜中As掺杂与锌的比例。
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