CN113363338A - 一种在GaAs衬底上生长GaInP薄膜的方法 - Google Patents
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- 239000000758 substrate Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229910001218 Gallium arsenide Inorganic materials 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 4
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- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 abstract description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910021617 Indium monochloride Inorganic materials 0.000 description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 4
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 4
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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- H01L31/03046—Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds including ternary or quaternary compounds, e.g. GaAlAs, InGaAs, InGaAsP
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- H01L31/184—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
- H01L31/1844—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP comprising ternary or quaternary compounds, e.g. Ga Al As, In Ga As P
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Abstract
本发明公开了一种在GaAs衬底上生长GaInP薄膜的方法。一、将具有2‑4º偏角的2英寸GaAs衬底清洗腐蚀；二、以金属Ga和金属In作为反应源，将Ga舟、In舟和衬底装炉并抽真空后通入H2，去除衬底表面杂质；三、将第一反应区的温度升入700‑800℃，通入HCl后，在第一反应区生成GaCl和InCl；四、将第二反应区的温度升入600‑660℃后关闭HCl，通入PH3后，在第二反应区生成GaInP薄膜；五、将第二反应区的温度降至室温后取样。采用HVPE工艺由于Ⅲ族反应源为有机源金属镓和金属铟且生长速度快，可以降低GaInP薄膜的制作成本，扩大电池的应用范围，使得太阳电池应用于地面领域成为可能。
Description
技术领域
本发明涉及半导体外延薄膜制备工艺，具体涉及一种在GaAs衬底上生长GaInP薄膜的方法。
背景技术
目前Si材料主要应用于空间站的太阳电池，光电转换效率为25.6%，但Si材料的光电转换效率已经接近理论极限值，不能满足人们对太阳电池的更高要求。人们逐渐将Ge、GaAs代替Si材料作为电池的基底，提高了太阳电池的光电转换效率至28.8%。后来在GaAs上制备GaInP薄膜进一步提高太阳电池的效率至37.9%。目前在GaAs上制备GaInP薄膜多为MOCVD工艺，但这种工艺的Ⅲ族反应源为有机源即三甲基镓（TMGa）和三甲基铟（TMIn），再加上生长速度慢，最终导致这种工艺制造的GaInP薄膜成本高昂，严重限制了电池的应用范围，无法进一步扩大其应用领域。
发明内容
鉴于现有技术存在的问题，本发明的目的是提供一种在GaAs衬底上生长GaInP薄膜的方法。该方法选择具有一定偏角的GaAs衬底上，利用HVPE（氢化物气相外延）方法制备出具有高生长速度和一定厚度的GaInP薄膜。
本发明采取的技术方案是：一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述方法有以下步骤：
一、将具有2-4º偏角的2英寸GaAs衬底清洗腐蚀，最后用去离子水清洗干净衬底表面残留溶液；腐蚀溶液：浓度为98%的H2SO4。
二、以金属Ga和金属In作为反应源，将Ga舟、In舟和衬底装炉并抽真空后通入H2，去除衬底表面杂质。
三、将第一反应区的温度升入700-800℃，压力保持为7000-8000Pa，通入流量为1.5-2sccm的HCl后，在第一反应区生成GaCl和InCl。
四、将第二反应区的温度升入600-660℃后关闭HCl，通入流量为100-200sccm的PH3后，在第二反应区生成GaInP薄膜。
五、将第二反应区的温度降至室温后取样。
所述步骤一中，腐蚀衬底一分钟。
所述步骤二中，通入H2三十分钟。
所述步骤三中，通入HCl十分钟。
所述步骤四中，通入PH3十分钟。
在HVPE GaInP制备过程中，以金属镓（Ga）和金属铟（In）为反应源，在第一反应区中通入10min的HCl生成GaCl和InCl，接着在第二反应区中通入10min的PH3反应生成GaInP。其中第一反应区为放置Ga舟和In舟的具有750-800℃的温区，第二反应区为具有600-660℃的温区，以下为反应方程式：
Ga(s)+HCl(g)=GaCl(g)+½H2(g)------------------------------ (1)
In(s)+HCl(g)=InCl(g)+½H2(g)-------------------------------(2)
GaCl(g)+ InCl(g)+PH3(g)= GaInP(g)+2HCl(g)+½H2(g)------------(3)
其中，反应方程式（1）、（2）发生在第一反应区；反应方程式（3）发生在第二反应区。
本发明所产生的有益效果是：本方法利用HVPE工艺特点，使用金属镓（Ga）和金属铟（In）代替传统制备工艺的三甲基镓（TMGa）和三甲基铟（TMIn）作为反应源，降低了制造成本，同时利用HVPE生长速度快的特点提高了GaInP的制备效率。采用HVPE工艺由于Ⅲ族反应源为有机源金属镓（Ga）和金属铟（In）且生长速度快，因此可以降低GaInP薄膜的制作成本，扩大电池的应用范围，使得太阳电池应用于地面领域成为可能。
附图说明
图1是本发明工艺流程图。
具体实施方式
以下结合附图和实施例对本发明作进一步说明。
如图1所示 ，1、衬底清洗：衬底为偏角2-4°的2英寸GaAs，先后用异丙醇、丙酮和酒精进行产生超声，接着用去离子水清洗干净残余溶液，再用浓度为98%的H2SO4溶液腐蚀衬底1分钟，最后用去离子水清洗干净衬底表面残留溶液。
2、以7N 金属Ga和金属In作为反应源，将Ga舟、In舟和衬底装炉并抽真空后通入30分钟的高纯H2去除衬底表面杂质。
3、接着将1区升温至750℃，压力保持为7000Pa，通10分钟HCl生成GaCl和InCl后关闭HCl，其中HCl（Ga）和HCl（In）流量为1.5 L/min；
4、将2区升温至600℃，通10分钟PH3气体后在GaAs衬底表面生成GaInP，反应结束后关闭PH3，其中PH3流量为150 L/min。
5、降至室温抽真空后升至常压后取样，最后利用型号为SUPRA 55VP的场发射扫描电子显微镜对样品进行能谱测试。
Claims (5)
1.一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述方法有以下步骤：
一、将具有2-4º偏了角的2英寸GaAs衬底清洗腐蚀，最后用去离子水清洗干净衬底表面残留溶液；腐蚀溶液：浓度为98%的H2SO4；
二、以金属Ga和金属In作为反应源，将Ga舟、In舟和衬底装炉并抽真空后通入H2，去除衬底表面杂质；
三、将第一反应区的温度升入700-800℃，压力保持为7000-8000Pa，通入流量为1.5-2sccm的HCl后，在第一反应区生成GaCl和InCl；
四、将第二反应区的温度升入600-660℃后关闭HCl，通入流量为100-200sccm的PH3后，在第二反应区生成GaInP薄膜；
五、将第二反应区的温度降至室温后取样。
2.根据权利要求1所述的一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述步骤一中，腐蚀衬底一分钟。
3.根据权利要求1所述的一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述步骤二中，通入H2三十分钟。
4.根据权利要求1所述的一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述步骤三中，通入HCl十分钟。
5.根据权利要求1所述的一种在GaAs衬底上生长GaInP薄膜的方法，其特征在于，所述步骤四中，通入PH3十分钟。
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Citations (5)
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| CN1588624A (zh) * | 2004-07-30 | 2005-03-02 | 中国科学院上海微系统与信息技术研究所 | 改进氢化物气相外延生长氮化镓结晶膜表面质量的方法 |
| CN101409233A (zh) * | 2007-10-05 | 2009-04-15 | 应用材料股份有限公司 | 用于沉积ⅲ/ⅴ族化合物的方法 |
| CN101809769A (zh) * | 2007-10-10 | 2010-08-18 | 信越半导体株式会社 | 化合物半导体外延晶片及其制造方法 |
| CN102912315A (zh) * | 2012-09-17 | 2013-02-06 | 南京大学 | 一种InN基薄膜材料生长方法 |
| CN203288608U (zh) * | 2013-06-07 | 2013-11-13 | 华南理工大学 | 生长在GaAs衬底上的InGaAs薄膜 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1588624A (zh) * | 2004-07-30 | 2005-03-02 | 中国科学院上海微系统与信息技术研究所 | 改进氢化物气相外延生长氮化镓结晶膜表面质量的方法 |
| CN101409233A (zh) * | 2007-10-05 | 2009-04-15 | 应用材料股份有限公司 | 用于沉积ⅲ/ⅴ族化合物的方法 |
| CN101809769A (zh) * | 2007-10-10 | 2010-08-18 | 信越半导体株式会社 | 化合物半导体外延晶片及其制造方法 |
| CN102912315A (zh) * | 2012-09-17 | 2013-02-06 | 南京大学 | 一种InN基薄膜材料生长方法 |
| CN203288608U (zh) * | 2013-06-07 | 2013-11-13 | 华南理工大学 | 生长在GaAs衬底上的InGaAs薄膜 |
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