CN104022164B - 一种应用于非晶Si太阳能电池的ZnO：Al绒面薄膜 - Google Patents
一种应用于非晶Si太阳能电池的ZnO：Al绒面薄膜 Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000004544 sputter deposition Methods 0.000 claims abstract description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
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- 239000000758 substrate Substances 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
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Abstract
本发明公开了一种利用CH3COONH4溶液腐蚀制备的应用于非晶Si太阳能电池中的绒面ZnO：Al透明导电薄膜的方法。该类绒面ZnO：Al薄膜由磁控溅射方法制备，靶材由高纯度的ZnO粉末和Al2O3粉末按一定比例混合烧结而成，薄膜生长温度为400℃，溅射功率为200W，溅射时间为45min。其次利用CH3COONH4溶液腐蚀得到的表面具有陨石坑的绒面ZnO：Al薄膜，其中CH3COONH4溶液的浓度为0.5～7.0wt％，腐蚀时间为5～30min。最后利用等离子体化学气相沉积(PECVD)沉积太阳能电池的吸光层(pin-Si层)。本发明制备的绒面ZnO：Al薄膜具有制备方法简单，易于操作，并且可以作为很好的非晶Si太阳能电池中的散光层，有利于提高非晶Si太阳能电池的效率。
Description
技术领域
本发明涉及一种应用于非晶Si太阳能电池的ZnO：Al绒面薄膜。
背景技术
目前的非晶Si基太阳能电池，自下而上依次包括衬底、透明导电薄膜、p型非晶Si、i型非晶Si、n型非晶Si和电极。现在市场上广泛应用的透明导电薄膜是ITO(In2O3:SnO2)和FTO(SnO2:F)材料，但由于地球上In的存储量很少，而且Sn4+元素容易被氢等离子体还原为Sn2+，这些直接导致了ITO和FTO长远应用的瓶颈。透明导电薄膜作为散射太阳光的窗口层，必须尽大可能散射太阳光，提高光的利用率，从而提高电池的效率。其中一个最重要的方法就是使得透明导电薄膜表面绒化，使其表面具有大小不均一的陨石坑结构，这样可以更有效地利用太阳光。然而，作为最常用的湿化学处理方法，尤其使用HCl、HNO3、NaOH等强酸强碱很难控制好薄膜表面的绒面结构。
发明内容
本发明的目的是提供一种方法简单，易于控制，成本低，光利用率高的非晶Si太阳能电池及其制备方法。
本发明的非晶Si太阳能电池，自下而上依次包括衬底、透明导电薄膜、p型非晶Si层、i型非晶Si层、n型非晶Si层和电极，其特征在于所述的透明导电薄膜是表面分布有直径在50～400nm的陨石坑的绒面ZnO：Al透明导电薄膜。
上述的衬底可以是蓝宝石、石英或玻璃。
所述的电极可以是Al、Ti或Au。
非晶Si太阳能电池中p型非晶Si层的厚度为20nm、i型非晶Si层的厚度为300nm、n型非晶Si层的厚度为30nm。
非晶Si太阳能电池的制备方法，其步骤如下：
(1)按Zn1-xAlxO化学式计量比，0.01≤X≤0.04，分别称取纯ZnO粉末和纯Al2O3粉末，将纯ZnO粉末和纯Al2O3粉末混合，研磨，在1000～1500℃烧结，制成ZnAlO基陶瓷靶材；
(2)采用磁控溅射方法，以步骤(1)的陶瓷靶作为靶材，在经清洗的衬底上沉积一层ZnO：Al薄膜；沉积条件为：衬底和靶材的距离为80mm，生长室真空度在2×10-3Pa以上，生长室通入纯Ar，控制压强为0.20Pa，调节溅射功率为200W，衬底温度为400℃，溅射时间为45min；
(3)将步骤(2)所得的沉积在衬上的ZnO：Al薄膜置于质量浓度为0.5～7.0％的CH3COONH4溶液中腐蚀5～30min，得到表面分布有陨石坑的绒面ZnO：Al薄膜；
(4)将步骤(3)所得的薄膜在450℃，Ar气氛中退火30min，然后采用等离子体化学气相沉积法在200℃下，按照以下条件依次沉积p-i-n层：a)通入SiH4,CH4,H2,B2H6反应气体沉积20nmp型硅碳薄膜，氢稀释比H2/SiH4为100∶1，SiH4与CH4流量比10∶1，沉积压力为100pa；b)通入SiH4,H2反应气体沉积300nmi型非晶Si层,H2/SiH4为10:1，沉积压强为100Pa；c)通入PH3、SiH4、H2气体沉积30nmn型非晶Si层，H2/SiH4为50:1；然后再镀上电极。
本发明中，所使用的纯ZnO粉末和纯Al2O3粉末的纯度均为99.99％。
本发明的优点在于：
(1)由于绒面ZnO:Al透明导电薄膜，其表面是大小不一的陨石坑，因此能够有效对可见光进行散射，增加太阳光的利用率。
(2)采用腐蚀方法制备绒面ZnO：Al透明导电薄膜重复性好，而且操作简便，成本低。制备的绒面ZnO：Al透明导电薄膜透过率在85％以上，能够满足太阳能电池器件的要求。
(3)利用绒面ZnO：Al透明导电薄膜作为非晶Si太阳能电池的窗口层，能够有效提高太阳能电池器件的光转换效率。
附图说明
图1为本发明的非晶Si太阳能电池示意图。图中：1为衬底，2为绒面ZnO：Al薄膜，3为p型非晶Si层，4为i型非晶Si层，5为n型非晶Si层，6为电极。
图2为ZnO：Al薄膜的扫描图。
图3为ZnO：Al薄膜的雾度图。
图4为非晶Si太阳能电池的电池效率图。
具体实施方式
以下结合附图及具体实例进一步说明本发明。
参照图1，本发明的非晶Si太阳能电池，自下而上依次包括衬底1、透明导电薄膜2、p型非晶Si层3、i型非晶Si层4、n型非晶Si层5和电极6，其中透明导电薄膜2是表面分布有直径在50～400nm的陨石坑的绒面ZnO：Al透明导电薄膜。
实例1：
(1)按Zn0.96Al0.04O化学式计量比Zn:Al＝0.96:0.04的比例，分别称取纯度为99.99％的ZnO粉末45.00g，纯度为99.99％的Al2O3粉末1.1747g。将称量好的ZnO粉末和Al2O3粉末倒入装有玛瑙球和乙醇的球磨罐中，在球磨机上球磨72个小时，使粉末细化并且均匀混合。然后将原料分离出来80℃烘干24小时，添加粘结剂研磨，压制成直径约3英寸，厚度3mm的圆片形。把成型的胚体放入烧结炉中，在1300℃烧结8小时，得到所需的Zn0.96Al0.04O基陶瓷靶材。
(2)采用磁控溅射方法，以步骤(1)的陶瓷靶作为靶材，在经清洗的玻璃衬底上沉积一层ZnO：Al薄膜。沉积条件为：衬底和靶材的距离为80mm，生长室真空度为2×10-3Pa，生长室通入纯Ar，控制压强为0.20Pa，调节溅射功率为200W，衬底温度为400℃，溅射时间为45min。
(3)将步骤(2)所得的ZnO：Al薄膜置于质量浓度为5.0％CH3COONH4溶液中腐蚀20min，腐蚀后的扫描图见图2。由图可见，绒面已经形成，并且陨石坑的直径在50～400nm，不均匀分布在绒面表面上。其雾度图见图3，由图可见在550nm处的雾度值为27％，表明太阳光可以有效被该种绒面薄膜散射。
(4)将步骤(3)所得的薄膜在450℃，Ar气氛围中退火30min，然后采用等离子体化学气相沉积法在200℃下，按照以下条件依次沉积pin层：a)通入SiH4,CH4,H2,B2H6反应气体沉积20nmp型硅碳薄膜，氢稀释比H2/SiH4为100∶1，SiH4与CH4流量比10∶1，沉积压力为100pa；b)通入SiH4,H2反应气体沉积300nmi型非晶Si层,H2/SiH4为10:1，沉积压强为100Pa；c)通入PH3、SiH4、H2气体沉积30nmn型非晶Si层，H2/SiH4为50:1，然后再镀上Al电极。图4为得到的非晶Si太阳能电池的电流-电压图，由图可见其光转换效率高达10.75％，表面绒面成功起到散射太阳光的效果。
实例2：
(1)按Zn0.98Al0.02O化学式计量比Zn:Al＝0.98:0.02的比例，分别称取纯度为99.99％的ZnO粉末45.00g，纯度为99.99％的Al2O3粉末0.5873g。将称量好的ZnO粉末和Al2O3粉末倒入装有玛瑙球和乙醇的球磨罐中，在球磨机上球磨72个小时，使粉末细化并且均匀混合。然后将原料分离出来80℃烘干24小时，添加粘结剂研磨，压制成直径约3英寸，厚度3mm的圆片形。把成型的胚体放入烧结炉中，在1300℃烧结8小时，得到所需的Zn0.98Al0.02O基陶瓷靶材。
(2)采用磁控溅射方法，以步骤(1)的陶瓷靶作为靶材，在经清洗的玻璃衬底上沉积一层ZnO：Al薄膜。沉积条件为：衬底和靶材的距离为80mm，生长室真空度为2×10-3Pa，生长室通入纯Ar，控制压强为0.20Pa，调节溅射功率为200W，衬底温度为400℃，溅射时间为45min。
(3)将步骤(2)所得的ZnO：Al薄膜置于质量浓度为3.0％CH3COONH4溶液中腐蚀20min，得到表面分布有陨石坑的绒面ZnO：Al薄膜，陨石坑的直径在50～300nm，并且不均匀分布在绒面表面上。其在550nm处的雾度值为6％。
(4)将步骤(3)所得的薄膜在450℃，Ar气氛围中退火30min，然后采用等离子体化学气相沉积法在200℃下，按照以下条件依次沉积pin层：a)通入SiH4,CH4,H2,B2H6反应气体沉积20nmp型硅碳薄膜，氢稀释比H2/SiH4为100∶1，SiH4与CH4流量比10∶1，沉积压力为100pa；b)通入SiH4,H2反应气体沉积300nmi型非晶Si层,H2/SiH4为10:1，沉积压强为100Pa；c)通入PH3、SiH4、H2气体沉积30nmn型非晶Si层，H2/SiH4为50:1，然后再镀上Au电极。所得到的非晶Si太阳能电池的光转换效率为9.05％。
实例3：
(1)按Zn0.96Al0.04O化学式计量比Zn:Al＝0.96:0.04的比例，分别称取纯度为99.99％的ZnO粉末45.00g，纯度为99.99％的Al2O3粉末1.1747g。将称量好的ZnO粉末和Al2O3粉末倒入装有玛瑙球和乙醇的球磨罐中，在球磨机上球磨72个小时，使粉末细化并且均匀混合。然后将原料分离出来80℃烘干24小时，添加粘结剂研磨，压制成直径约3英寸，厚度3mm的圆片形。把成型的胚体放入烧结炉中，在1300℃烧结8小时，得到所需的Zn0.96Al0.04O基陶瓷靶材。
(2)采用磁控溅射方法，以步骤(1)的陶瓷靶作为靶材，在经清洗的蓝宝石衬底上沉积一层ZnO：Al薄膜。沉积条件为：衬底和靶材的距离为80mm，生长室真空度为2×10-3Pa，生长室通入纯Ar，控制压强为0.20Pa，调节溅射功率为200W，衬底温度为400℃，溅射时间为45min。
(3)将步骤(2)所得的ZnO：Al薄膜置于质量浓度为5.0％CH3COONH4溶液中腐蚀5min，得到表面分布有陨石坑的绒面ZnO：Al薄膜，陨石坑的直径在50～350nm，并且不均匀分布在绒面表面上。其在550nm处的雾度值为9％。
(4)将步骤(3)所得的薄膜在450℃，Ar气氛围中退火30min，然后采用等离子体化学气相沉积法在200℃下，按照以下条件依次沉积pin层：a)通入SiH4,CH4,H2,B2H6反应气体沉积20nmp型硅碳薄膜，氢稀释比H2/SiH4为100∶1，SiH4与CH4流量比10∶1，沉积压力为100pa；b)通入SiH4,H2反应气体沉积300nmi型非晶Si层,H2/SiH4为10:1，沉积压强为100Pa；c)通入PH3、SiH4、H2气体沉积30nmn型非晶Si层，H2/SiH4为50:1，然后再镀上Ti电极。所得到的非晶Si太阳能电池的光转换效率为8.27％。
Claims (1)
1.一种非晶Si太阳能电池的制备方法，其步骤如下：
(1)按Zn1-xAlxO化学式计量比，0.01≤X≤0.04，分别称取纯ZnO粉末和纯Al2O3粉末，将纯ZnO粉末和纯Al2O3粉末混合，研磨，在1000～1500℃烧结，制成ZnAlO基陶瓷靶材；
(2)采用磁控溅射方法，以步骤(1)的陶瓷靶作为靶材，在经清洗的衬底上沉积一层ZnO：Al薄膜；沉积条件为：衬底和靶材的距离为80mm，生长室真空度在2×10-3Pa以上，生长室通入纯Ar，控制压强为0.20Pa，调节溅射功率为200W，衬底温度为400℃，溅射时间为45min；
(3)将步骤(2)所得的沉积在衬上的ZnO：Al薄膜置于质量浓度为0.5～7.0％的CH3COONH4溶液中腐蚀5～30min，得到表面分布有陨石坑的绒面ZnO：Al薄膜；
(4)将步骤(3)所得的薄膜在450℃，Ar气氛中退火30min，然后采用等离子体化学气相沉积法在200℃下，按照以下条件依次沉积p-i-n层：a)通入SiH4,CH4,H2,B2H6反应气体沉积20nmp型硅碳薄膜，氢稀释比H2/SiH4为100∶1，SiH4与CH4流量比10∶1，沉积压力为100pa；b)通入SiH4,H2反应气体沉积300nmi型非晶Si层,H2/SiH4为10:1，沉积压强为100Pa；c)通入PH3、SiH4、H2气体沉积30nmn型非晶Si层，H2/SiH4为50:1；然后再镀上电极。
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