CN112030143A - 一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法 - Google Patents
一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法 Download PDFInfo
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- 229910021417 amorphous silicon Inorganic materials 0.000 title claims abstract description 88
- 238000002161 passivation Methods 0.000 title claims abstract description 52
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims abstract description 14
- 239000012495 reaction gas Substances 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000151 deposition Methods 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- 238000010790 dilution Methods 0.000 claims abstract description 3
- 239000012895 dilution Substances 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 230000008021 deposition Effects 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 239000000758 substrate Substances 0.000 abstract description 9
- 229910021421 monocrystalline silicon Inorganic materials 0.000 abstract description 7
- 238000000137 annealing Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
本发明公开一种用于a‑Si/c‑Si异质结太阳电池的高效非晶硅钝化膜的制备方法，用等离子体增强化学气相沉积(PECVD)方法，以SiH4、H2为反应气体，将单晶硅衬底放入PECVD腔室，在单晶硅衬底上两步法沉积制备非晶硅薄膜，包括以下两个主要步骤：a)以纯SiH4为反应气体，在高耗尽率状态下生长非晶硅缓冲层；b)以高氢稀释比的SiH4和H2的混合气体为反应气体，在非晶硅钝化缓冲层上生长非晶硅钝化膜。本发明利用PECVD方法，采用两步法完成非晶硅钝化膜的制备，大大提高了a‑Si/c‑Si异质结太阳电池的界面钝化质量，少子寿命显著提高，且制备时间段、工艺简单，同时无需特别退火，降低成本。
Description
技术领域
本发明属于太阳电池领域，是一种用于a-Si/c-Si异质结太阳电池中c-Si表面钝化的非晶硅薄膜的制备方法。
背景技术
近年来，能源紧缺问题和全球变暖的环境问题日益严重，人类对清洁的可再生能源需求空前急切。光伏太阳能是一种重要的可再生能源，具有能源广泛，地域限制少，安全可靠等诸多优势。
自1954年第一块硅太阳电池应用至今，太阳电池经过了第一代单晶硅太阳电池，第二代薄膜电池的发展，但是当前高的发电成本仍然严重限制太阳电池的进一步广泛应用，因此降低太阳电池成本成为当前研究的重点。从目前光伏太阳电池的发展来看，其技术发展趋势是成本降低，效率提高。
带有本征薄层(本发明所制备的非晶钝化层)的a-Si/c-Si异质结太阳电池目前最高转换效率高达25.6％，保持晶硅太阳电池的世界纪录。但是a-Si/c-Si异质结太阳电池的技术难度很高，特别是高质量钝化膜的制备更是a-Si/c-Si异质结太阳电池的最关键技术。
发明内容
本发明解决的技术问题是：提供一种用于a-Si/c-Si异质结太阳电池中c-Si 表面钝化的非晶硅薄膜的制备方法，本发明利用等离子体增强化学气相沉积 (PECVD)方法，通过技术创新采用两步法完成非晶硅钝化膜的制备，大大提高了a-Si/c-Si异质结太阳电池的界面钝化质量，少子寿命显著提高。这种方法制备时间段、工艺简单，同时无需特别退火，在降低成本方面也有显著优势。
本发明采用的技术方案如下：
一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，用等离子体增强化学气相沉积(PECVD)方法，以SiH4、H2为反应气体，将单晶硅衬底放入PECVD腔室，在单晶硅衬底上两步法沉积制备非晶硅薄膜，其特征在于，包括以下两个主要步骤：a)以纯SiH4为反应气体，在高耗尽率状态下生长非晶硅缓冲层；b)以高氢稀释比的SiH4和H2的混合气体为反应气体，在非晶硅钝化缓冲层上生长非晶硅钝化膜。
优选的，所述步骤a)中，非晶硅缓冲层的制备为在高耗尽的硅烷等离子下生长，射频或甚高频功率密度小于等于100mW/cm2。
优选的，所述步骤a)中，非晶硅缓冲层的制备为在高耗尽的硅烷等离子下生长，且射频或甚高频功率密度为30mW/cm2-100mW/cm2。
优选的，所述步骤a)中，生长所述非晶硅缓冲层的沉积速率应大于等于 0.5nm/，所述的非晶硅缓冲层的厚度为1～5nm。
优选的，所述步骤a)生长完所述非晶硅缓冲层后，以及步骤b)生长所述非晶硅钝化层之前，PECVD腔室不破空。
优选的，所述步骤b)中H2与SiH4的流量比为3:1-20:1。
优选的，所述步骤b)中H2与SiH4的流量比为10:1。
优选的，所述步骤b)中，在非晶硅钝化缓冲层上生长非晶硅钝化膜的射频或甚高频功率密度在100mW/cm2-300mW/cm2之间。
优选的，所述步骤b)中，在非晶硅钝化缓冲层上生长非晶硅钝化膜的厚度大于等于3nm。
本发明的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，能够显著提高a-Si/c-Si异质结太阳电池的少子寿命，从常规工艺的500-600us 提高到4ms，电池效率得到明显提高；并且制备方法简单、高效，无需退火工艺，大大降低了能耗。另外本发明提出的工艺与现有a-Si/c-Si异质结太阳电池的制备工艺完全兼容，利于产业化发展。
具体实施方式
下面结合说明和实施例对本发明作进一步说明，本发明的方式包括但不仅限于以下实施例。
实施例1
(1)以纯SiH4为反应气体，洁净的单晶硅衬底上沉积非晶硅缓冲层。甚高频等离子体增强化学气相沉积(VHF-PECVD)制备缓冲层的条件为：背底真空高于10-3Pa，衬底温度200℃，气体SiH4流量为15sccm，压强为0.4mbar，沉积功率50mW/cm2，制备的非晶硅缓冲层的厚度2nm。
(2)接着在非晶硅缓冲层表面生长非晶硅钝化膜。VHF-PECVD制备缓冲层的条件为：背底真空高于10-3Pa，衬底温度200℃，气体SiH4流量为15sccm，气体H2流量为150sccm，压强为0.5mbar，沉积功率150mW/cm2，制备的非晶硅钝化层的厚度4nm。
对比例1：
以纯SiH4为反应气体，洁净的单晶硅衬底上沉积非晶硅钝化膜。甚高频等离子体增强化学气相沉积(VHF-PECVD)制备非晶硅钝化膜的条件为：背底真空高于10-3Pa，衬底温度200℃，气体SiH4流量为15sccm，压强为0.4mbar，沉积功率50mW/cm2，制备的非晶硅钝化层的厚度6nm。
对比例2：
在洁净的单晶硅衬底上，生长非晶硅钝化膜。VHF-PECVD制备非晶硅钝化膜的条件为：背底真空高于10-3Pa，衬底温度230℃，气体SiH4流量为15sccm，气体H2流量为150sccm，压强为0.5mbar，沉积功率150mW/cm2，制备的非晶硅钝化层的厚度6nm。
测试一：对实施例和对比例中的非晶硅钝化膜的钝化效果进行少子寿命测试：
一、测试条件：采用Sinton WCT-120仪器测试，运用Transient模式进行测试，160μm绒面N型单晶硅(5-10Ωcm)，两面制备实施例及对比例所属的非晶硅钝化层。
二、测试方法：采用Transient模式。Transient模式对非晶硅钝化膜的钝化效果进行少子寿命测试为本领域技术所熟知的常规测试手段，在这里不再进行详细的阐述。
测试二：对实施例和对比例中采用不同非晶硅钝化膜工艺的太阳能电池进行IV测试。
一、太阳能电池的制备工艺：包括如下步骤：清洗、制绒、制备非晶硅钝化膜、制备发射极及背场、制备TCO、印刷并烘干电极。上述太阳电池的制备工艺除非晶硅钝化膜工艺采用本发明的实施例和对比例工艺制备，其余工艺相同且同一炉进行制备。上述太阳能电池除非晶硅钝化膜工艺采用本发明的实施例和对比例工艺制备，其余工艺步骤皆为现有太阳能电池制备工艺，为本领域技术人员所熟知，因此，在这里不再进行详细的阐述。
二、太阳能电池板IV测试条件：测试温度为25℃，AM1.5光谱，光强1000W/m2。
上述少子寿命测试和IV测试的测试结果如下表1所示：
表1性能测试结果
需要指出的是，上述关于制备步骤的具体实施例方式仅为简单清楚描述本发明原理的示意性举例，并非对本发明作任何形式上的限制，尤其是一些可通过现有工艺实现的步骤。
虽然本发明已以较佳实施例揭露如上，然而并非用以限定本发明。本领域普通技术人员显然可知，在不脱离本发明技术方案范围内，当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例，但是未脱离本发明技术方案的内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均仍属于本发明技术方案的范围内。
Claims (9)
1.一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，用等离子体增强化学气相沉积(PECVD)方法，以SiH4、H2为反应气体，将单晶硅衬底放入PECVD腔室，在单晶硅衬底上两步法沉积制备非晶硅薄膜，其特征在于，包括以下两个主要步骤：a)以纯SiH4为反应气体，在高耗尽率状态下生长非晶硅缓冲层；b)以高氢稀释比的SiH4和H2的混合气体为反应气体，在非晶硅钝化缓冲层上生长非晶硅钝化膜。
2.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤a)中，非晶硅缓冲层的制备为在高耗尽的硅烷等离子下生长，射频或甚高频功率密度小于等于100mW/cm2。
3.根权利要求2中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤a)中，非晶硅缓冲层的制备为在高耗尽的硅烷等离子下生长，且射频或甚高频功率密度为30mW/cm2-100mW/cm2。
4.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤a)中，生长所述非晶硅缓冲层的沉积速率应大于等于0.5nm/，所述的非晶硅缓冲层的厚度为1～5nm。
5.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤a)生长完所述非晶硅缓冲层后，以及步骤b)生长所述非晶硅钝化层之前，PECVD腔室不破空。
6.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤b)中H2与SiH4的流量比为3:1-20:1。
7.根权利要求6中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤b)中H2与SiH4的流量比为10:1。
8.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤b)中，在非晶硅钝化缓冲层上生长非晶硅钝化膜的射频或甚高频功率密度在100mW/cm2-300mW/cm2之间。
9.根权利要求1中所述的一种用于a-Si/c-Si异质结太阳电池的高效非晶硅钝化膜的制备方法，其特征在于，所述步骤b)中，在非晶硅钝化缓冲层上生长非晶硅钝化膜的厚度大于等于3nm。
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