CN101861213A - 等离子体处理的光伏器件 - Google Patents

等离子体处理的光伏器件 Download PDF

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CN101861213A
CN101861213A CN200980100068A CN200980100068A CN101861213A CN 101861213 A CN101861213 A CN 101861213A CN 200980100068 A CN200980100068 A CN 200980100068A CN 200980100068 A CN200980100068 A CN 200980100068A CN 101861213 A CN101861213 A CN 101861213A
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semiconductor layer
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大卫·伊格尔沙姆
安克·阿肯
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First Solar Inc
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Abstract

一种制造薄膜光伏器件的方法包括：在基底上沉积第一化合物半导体层，并使该器件暴露于等离子体，等离子体处理该层。

Description

等离子体处理的光伏器件
本申请要求于2008年1月15日提交的第61/021,156号美国临时专利申请的优先权，该申请通过引用全部包含于此。
技术领域
本发明涉及光伏电池。
背景技术
在光伏器件的制造过程中，由半导体材料制成的层包括吸收层，在吸收层中光能被转化为电能。一些光伏器件可以使用同样是电荷的导体的透明薄膜。导电薄膜可以是诸如掺氟氧化锡、掺铝氧化锌或氧化铟锡的透明导电氧化物(TCO)。TCO可以允许光穿过而到达活性光吸收材料，并且还起到欧姆接触的作用来传送光生载流子离开光吸收材料。可以在半导体层的后表面上形成背电极。背电极可以包含诸如金属银、镍、铜、铝、钛、钯或它们的任一实际组合的导电材料，以提供与半导体层的电连接。背电极也可以是半导体材料或透明导电氧化物。掺杂半导体层可以提高光伏器件的效率。
发明内容
一种制造薄膜光伏器件的方法可以包括：在基底上沉积第一化合物半导体层；使所述器件暴露于等离子体，等离子体处理所述层。制造薄膜光伏器件的方法还可以包括：将诸如背金属接触的背接触涂敷于所述化合物半导体层。
在一些情况下，可以在涂敷背金属接触之前进行等离子体处理。在其他情况下，可以在涂敷背接触之后进行等离子体处理。
制造薄膜光伏器件的方法还可以包括在基底之上涂敷透明导电层。制造薄膜光伏器件的方法还可以包括在第一化合物半导体层之上涂敷第二化合物半导体层。制造薄膜光伏器件的方法还可以包括设置连接到光伏器件的电连接，用来采集由光伏器件产生的电能。
在一些情况下，制造薄膜光伏器件的方法可以包括在等离子体处理之前使所述化合物半导体层暴露于氯化镉处理。例如，等离子体处理可以进行大约5分钟、大约10分钟、大约15分钟、大约20分钟、大约25分钟或大约30分钟。等离子体处理可以包括活性离子蚀刻。可以在真空中进行等离子体处理。可以在大气压力下进行等离子体处理。
一种化合物半导体基光伏器件可以包括：基底；等离子体处理的化合物半导体层，位于基底上。等离子体可以包括氢等离子体、氮等离子体、氩等离子体、氦等离子体或氧等离子体混合物。
化合物半导体可以是碲化镉。化合物半导体可以是铜铟硫化物、铜铟镓二硒化物或铜铟镓二硒硫化物。化合物半导体可以是硫化镉。基底可以是玻璃。
化合物半导体基光伏器件还可以包括在半导体层之上的背金属接触。化合物半导体基光伏器件还可以包括在基底之上的透明导电层。化合物半导体基光伏器件还可以包括在第一化合物半导体层之上的第二化合物半导体层。
一种用来产生电能的系统可以包括：多层光伏器件，所述光伏器件包括基底和位于基底上的等离子体处理的第一化合物半导体层；电连接，连接到光伏器件，用来采集由光伏器件产生的电能。
附图说明
图1是等离子体处理的光伏器件的示意图。
图2是等离子体处理的光伏器件的示意图。
图3是等离子体处理的光伏器件的示意图。
图4是等离子体处理的光伏系统的示意图。
图5是用于对基底进行等离子体处理的系统的示意图。
具体实施方式
光伏电池可以包括在基底表面上的透明导电层、第一半导体层、支撑半导体层的基底和与半导体层接触的金属层。可以用合适的等离子体处理来处理光伏电池。
参照图1，一种制造薄膜光伏器件的方法可以包括：在基底120上沉积化合物半导体层110，并使该器件暴露于等离子体100(等离子体对该层进行处理)，从而生成在基底220上包括等离子体处理的半导体层210的光伏器件。制造薄膜光伏器件的方法还可以包括将背金属接触(back metal contact)涂敷于化合物半导体层。在一些情况下，可以在涂敷背金属接触前执行等离子体处理。在其它情况下，可以在涂敷背金属接触后执行等离子体处理。例如，可以执行等离子体处理大约5分钟、大约10分钟、大约15分钟、大约20分钟、大约25分钟或者大约30分钟。也可以执行其它的时间设定。
参照图2，一种制造薄膜光伏器件的方法也可以包括在基底330之上涂敷透明导电层320。可以在透明导电层之上沉积第一化合物半导体层310。这种制造薄膜光伏器件的方法还可以包括在第一化合物半导体层之上涂敷第二化合物半导体层340。可以在等离子体处理500前使任一化合物半导体层经受氯化镉处理400。可以执行等离子体处理大约5至20分钟，从而对半导体层进行处理。等离子体处理可以包括活性离子蚀刻。可以在真空中进行等离子体处理。可以在大气压力下进行等离子体处理。
参照图3，一种制造薄膜光伏器件的方法也可以包括在基底530之上涂敷透明导电层520。可以在透明导电层之上沉积第一化合物半导体层510。这种制造薄膜光伏器件的方法还可以包括在第一化合物半导体层之上涂敷第二化合物半导体层540。第一化合物半导体层或第二化合物半导体层可以是等离子体处理的层。该方法还可以包括在等离子体处理的层之上设置诸如背金属接触的背接触550。这种制造薄膜光伏器件的方法还可以包括设置连接到背金属接触的电连接560A和连接到透明导电层的电连接560B，电连接560A和560B分别用来采集由光伏器件产生的电能。背接触可以是等离子体处理的层。
参照图4，一种产生电能的系统可以包括：多层光伏器件，该多层光伏器件包括在基底630之上的透明导电层620、在透明导电层之上的等离子体处理的化合物半导体层610、在等离子体处理的化合物半导体层之上的背金属接触650；分别连接到背接触和透明导电层的电连接660A和660B。背接触可以是等离子体处理的层。
在一些情况下，系统还可以包括在第一化合物半导体层之上的第二化合物半导体层640。第二化合物半导体层可以在背金属接触和第一化合物半导体层之间。
参照图5，可以利用沉积系统来制造光伏电池。沉积系统可以包括被构造成在基底上设置半导体涂层的分布器(distributor)、被构造成加热分布器的第一电源和紧挨着分布器的等离子体源，等离子体源包括被构造成驱动等离子体源的电极，其中，电极与第一电源是电学独立的。例如，分布器可以是包括套管(sheath tube)34(例如，陶瓷套管)的组件。一方面，分布器可以是包括套管、加热器和供给管的组件。陶瓷套管可以包住加热器24(例如，可渗透加热器)，加热器反过来可以包住供给管。套管可以包括一个或多个被构造成在基底8上提供半导体涂层的分布孔36。等离子体源可以包括被构造成驱动等离子体源的电极。系统还可以包括被构造成使等离子体源相对于基底偏压的附加电极。在特定情况下，分布器可以包括一对套管。在一个实施例中，电极可以是第一套管和第二套管之间的隔离物。隔离物可以包括石墨横杆电极(graphite cross-rod electrode)。隔离物可以包含诸如碳的非金属材料或者其它耐腐蚀的材料。在一个实施例中，隔离物可以是石墨隔离物。附加电极可以是套管之上的背帽(backcap)4。背帽可以是石墨背帽。绝缘件可以位于隔离物和石墨背帽之间。
在一些情况下，该系统或方法可以包括被构造成使等离子体源相对于基底偏压的附加电极。电极可以是分布器之上的背帽。例如，电极可以包含诸如碳的非金属材料。在一个实施例中，电极可以包含石墨。电极可以是隔离物。电极可以是背帽。隔离物可以是石墨隔离物。背帽可以是石墨背帽。
在其它情况下，分布器可以包括一对套管，这对套管包括第一套管和第二套管。电极可以是第一套管和第二套管之间的隔离物。电极可以是第一套管和第二套管之上的背帽。
前面的方法已经包括在多晶硅基太阳能电池装置和具有氮化硅栅极电介质/非晶硅半导体界面的薄膜晶体管中的氢等离子体处理。例如参见：美国专利5,273,920；美国专利5,281,546；M.J.Keeves，A.Turner，U.Schubert，P.A.Basore，M.A.Green，20th EU Photovoltaic Solar Energy Conf.(第20届欧洲光伏太阳能会议)，Barcelona(巴塞罗那)(2005)，p 1305-1308；P.A.Basore，4th World Conf.Photovoltaic Energy Conversion(第4届世界光伏能量转换大会)，Hawaii(夏威夷)(2006)，p 2089-2093，上述文献通过引用包含于此。然而，等离子体处理没有应用于化合物半导体(即，碲化镉或铜铟镓二硒硫化物)基光伏电池。
化合物半导体基光伏器件可以包括基底和基底上的等离子体处理的化合物半导体层。等离子体可以包括氢等离子体、氮等离子体、氩等离子体、氦等离子体或氧等离子体混合物。化合物半导体可以是碲化镉。化合物半导体可以是铜铟硫化物、铜铟镓二硒化物或铜铟镓二硒硫化物。化合物半导体可以是硫化镉。基底可以是玻璃。化合物半导体基光伏器件还可以包括在半导体层之上的背接触(例如，背金属接触)。化合物半导体基光伏器件还可以包括在基底之上的透明导电层。化合物半导体基光伏器件还可以包括在第一化合物半导体层之上的第二化合物半导体层。
可以在真空中或大气压力下对化合物半导体膜执行等离子体处理。等离子体处理可以作为蚀刻工艺的一部分。等离子体处理也可以用作表面、界面或中间间隙状态钝化工艺的一部分，以改善电传输特性、粘附特性和接触特性。等离子体处理可以用来提高在操作条件下的长期器件性能。
可以在化学处理前后或者在接触涂敷之前将半导体层暴露于等离子体。
在一个示例中，包括CdTe层的薄膜光伏器件的10×10cm2样品在CdCl2处理之后暴露于氢等离子体处理。氢等离子体功率设定在50W至200W之间并且处理时间为5分钟至20分钟。将室压力保持在300毫托(mTorr)下不变。结果包括Roc值减小，典型的是，对于等离子体处理的器件的Roc值比对于未经处理的器件所发现的Roc值下降了0.2欧姆-8欧姆，表明电接触特性得以改善。器件暴露于光(1AM)和热(110摄氏度-115摄氏度)下的应力测试。在经受28天的应力暴露之后，氢等离子体处理的器件比标准器件表现出更高的最终转换效率(达1.5)和减小了的Roc值(典型的，下降了0.2欧姆-8欧姆)。
普通的光伏电池可以具有多层。多层可以包括作为透明导电层的底层、覆盖层(capping layer)、窗口层、吸收层和顶层。可以按要求在生产线的不同沉积台沉积每一层，其中，生产线在每个台都具有单独的沉积气体供应和真空密封的沉积室。可以通过滚动传送器将基底从一个沉积台传送至另一个沉积台，直到沉积了所有期望的层。可以利用诸如溅射的其它技术来添加另外的层。导电体可以分别连接到顶层和底层，以采集在太阳能量入射到吸收层上时产生的电能。可以在顶层的顶部上布置顶部基底层，以形成夹层结构，从而完成光伏电池。
底层可以是透明导电层，并且例如可以是诸如氧化锡或掺杂有氟的氧化锡的透明导电氧化物。在高温下直接在透明导电氧化物层上沉积半导体层会导致对光伏器件的性能和稳定性产生负面影响的反应。沉积化学稳定性高的材料(例如，二氧化硅、三氧化二铝、二氧化钛、三氧化二硼和其它类似物质)的覆盖层可以明显减小这些反应对器件性能和稳定性的影响。因为使用的材料的电阻率高，所以应当将覆盖层的厚度最小化。否则，可能发生与期望的电流流动反向的电阻块(resistive block)。通过填充表面的不规则性，覆盖层可以降低透明导电氧化物层的表面粗糙程度，这会有助于窗口层的沉积并且可以使窗口层能够具有更薄的横截面。降低的表面粗糙程度可以有助于改善窗口层的一致性。在光伏电池中包括覆盖层的其他优点可以包括改善光学清晰度、改善带隙的连续性、在接合点提供更好的场强以及提供更好的由于开路电压损失所测量的器件效率。例如，在第20050257824号美国专利公开中描述了覆盖层，该专利公开通过引用全部包含于此。
窗口层和吸收层例如可以包含诸如II族-VI族、III族-V族或IV族半导体的二元半导体，例如，ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、InS、TlN、TlP、TlAs、TlSb或者它们的混合物或合金。窗口层和吸收层的示例是由CdTe层涂覆的CdS层。顶层可以覆盖半导体层。例如，顶层可以包含诸如铝、钼、铬、钴、镍、钛、钨或它们的合金的金属。顶层也可以包含金属氧化物或金属氮化物或它们的合金。
例如，在第5,248,349、5,372,646、5,470,397、5,536,333、5,945,163、6,037,241和6,444,043号美国专利中描述了在光伏器件的制造中半导体层的沉积，所述美国专利通过引用全部包含于此。沉积可以包括蒸气从源到基底的传输，或者固体在密闭体系中的升华。用于制造光伏电池的设备可以包括传送器，例如具有辊子的滚动传送器。其他类型的传送器是可用的。传送器将基底传送到一串的一个或多个沉积台，所述沉积台用来在基底的暴露表面上沉积材料层。在第11/692,667号美国临时申请中描述了传送器，该申请通过引用包含于此。
可以加热沉积室以达到不低于约450℃且不高于约700℃的处理温度，例如温度可以在450℃-550℃、550℃-650℃、570℃-600℃、600℃-640℃的范围或在其他任何高于450℃且低于约700℃的范围。沉积室包括连接到沉积蒸气供应器的沉积分布器。可以将分布器连接到用于不同层的沉积的多个蒸气供应器，或者可以将基底移动通过具有其自身的蒸气分布器和供应器的多个不同沉积台。分布器可以是具有不同喷嘴尺寸的喷雾嘴的形式，以有助于蒸气供应的均匀分布。
光伏电池的底层可以是透明导电层。薄的覆盖层可以在透明半导体层的顶部上，并且至少部分地覆盖透明半导体层。沉积的下一层是第一半导体层，第一半导体层可以用作窗口层并且可以根据透明导电层和覆盖层的用途而更薄。沉积的下一层是第二半导体层，第二半导体层用作吸收层。其他层，例如包含掺杂剂的层，可以在整个制造过程中根据需要而沉积或者布置在基底上。
透明导电层可以是透明导电氧化物(例如像氧化锡这样的金属氧化物)，其可以被例如氟掺杂。透明导电层可以沉积在前接触和第一半导体层之间，并且可以具有足够高的电阻以减小第一半导体层中的针孔效应。第一半导体层中的针孔会导致在第二半导体层和第一接触之间形成分流(shunt)，导致围绕针孔的局部场上的漏端(drain)。该通路的电阻的微小增加可以显著地减少受到分流影响的区域。
可以提供覆盖层以供应电阻的这种增加。覆盖层可以是由化学稳定性高的材料制成的非常薄的层。覆盖层与厚度可与之比较的具有相同厚度的半导体材料相比，可以具有更高的透明度。适合用作覆盖层的材料的示例包括二氧化硅、三氧化二铝、二氧化钛、三氧化二硼和其他类似物质。覆盖层还可以起到将透明导电层与第一半导体层电学且化学地隔离的作用，从而防止在高温下出现的会对性能和稳定性产生负面影响的反应。覆盖层还可以提供可以更适合接受第一半导体层的沉积的导电表面。例如，覆盖层可以提供降低了表面粗糙程度的表面。
第一半导体层可以用作第二半导体层的窗口层。第一半导体层可以比第二半导体层薄。由于第一半导体层比第二半导体层薄，第一半导体层可以使波长更短的入射光能够更大程度地穿透至第二半导体层。
第一半导体层例如可以是II族-VI族、III族-V族或IV族半导体，例如，ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、InS、TlN、TlP、TlAs、TlSb或者它们的混合物或合金。第一半导体层可以是二元半导体，例如其可以是CdTe。第二半导体层可以沉积到第一半导体层上。当第一半导体层用作窗口层时，第二半导体层可以用作对入射光的吸收层。与第一半导体层相似，第二半导体层例如也可以是II族-VI族、III族-V族或IV族半导体，例如，ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、MgO、MgS、MgSe、MgTe、HgO、HgS、HgSe、HgTe、MnO、MnS、MnTe、AlN、AlP、AlAs、AlSb、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb、InS、TlN、TlP、TlAs、TlSb或者它们的混合物或合金。第一半导体层或第二半导体层例如也可以是III族-VI族半导体，例如，铜铟硫化物、铜铟镓二硒化物、铜铟镓二硒硫化物或者它们的混合物或合金。
第二半导体层可以沉积到第一半导体层上。覆盖层可以用来使透明导电层与第一半导体层电学地且化学地隔离，从而防止在高温下出现的会对性能和稳定性产生负面影响的反应。透明导电层可以沉积在基底上。
已经描述了多个实施例。然而，应该理解的是，在不脱离本发明的精神和范围的情况下可以做出各种修改。例如，半导体层可以包括多种可以用于缓冲层和覆盖层的材料的其他材料。因此，其他实施例在权利要求的范围之内。

Claims (42)

1.一种制造薄膜光伏器件的方法，所述方法包括以下步骤：
在基底上沉积化合物半导体层；
使所述器件暴露于等离子体，等离子体处理所述层。
2.如权利要求1所述的方法，所述方法还包括：将背接触涂敷到化合物半导体层上。
3.如权利要求2所述的方法，其中，在涂敷背接触之前进行等离子体处理。
4.如权利要求2所述的方法，其中，在涂敷背接触之后进行等离子体处理。
5.如权利要求1所述的方法，所述方法还包括在基底之上涂敷透明导电层。
6.如权利要求1所述的方法，所述方法还包括在化合物半导体层之上涂敷透明导电层。
7.如权利要求1所述的方法，所述方法还包括在化合物半导体层之上涂敷第二化合物半导体层。
8.如权利要求1所述的方法，所述方法还包括设置连接到光伏器件的电连接，用来采集由光伏器件产生的电能。
9.如权利要求1所述的方法，所述方法还包括在等离子体处理之前使化合物半导体层经受氯化镉处理。
10.如权利要求1所述的方法，其中，等离子体处理进行大约5分钟。
11.如权利要求1所述的方法，其中，等离子体处理进行大约10分钟。
12.如权利要求1所述的方法，其中，等离子体处理进行大约20分钟。
13.如权利要求1所述的方法，其中，等离子体处理进行大约30分钟。
14.如权利要求1所述的方法，其中，等离子体处理包括活性离子蚀刻。
15.如权利要求1所述的方法，其中，在真空中进行等离子体处理。
16.如权利要求1所述的方法，其中，在大气压力下进行等离子体处理。
17.一种化合物半导体基光伏器件，所述器件包括：
基底；
等离子体处理的化合物半导体层，位于基底上。
18.如权利要求17所述的光伏器件，其中，等离子体包括氢等离子体。
19.如权利要求17所述的光伏器件，其中，等离子体包括氮等离子体。
20.如权利要求17所述的光伏器件，其中，等离子体包括氩等离子体。
21.如权利要求17所述的光伏器件，其中，等离子体包括氦等离子体。
22.如权利要求17所述的光伏器件，其中，等离子体包括氧等离子体。
23.如权利要求17所述的光伏器件，其中，化合物半导体是碲化镉。
24.如权利要求17所述的光伏器件，其中，化合物半导体是铜铟硫化物、铜铟镓二硒化物或铜铟镓二硒硫化物。
25.如权利要求17所述的光伏器件，其中，基底为玻璃。
26.如权利要求17所述的光伏器件，所述器件还包括在半导体层之上的背金属接触。
27.如权利要求17所述的光伏器件，所述器件还包括在基底之上的透明导电层。
28.如权利要求17所述的光伏器件，所述器件还包括在化合物半导体层之上的透明导电层。
29.如权利要求17所述的器件，所述器件还包括在化合物半导体层之上的第二化合物半导体层。
30.一种用于产生电能的系统，所述系统包括：
多层光伏器件，所述光伏器件包括基底和位于基底上的等离子体处理的化合物半导体层；
电连接，连接到光伏器件，用来采集由光伏器件产生的电能。
31.如权利要求30所述的系统，其中，等离子体包括氢等离子体。
32.如权利要求30所述的系统，其中，等离子体包括氮等离子体。
33.如权利要求30所述的系统，其中，等离子体包括氩等离子体。
34.如权利要求30所述的系统，其中，等离子体包括氦等离子体。
35.如权利要求30所述的系统，其中，等离子体包括氧等离子体。
36.如权利要求30所述的系统，其中，化合物半导体是碲化镉。
37.如权利要求30所述的系统，其中，化合物半导体是铜铟硫化物、铜铟镓二硒化物或铜铟镓二硒硫化物。
38.如权利要求30所述的系统，其中，基底为玻璃。
39.如权利要求30所述的系统，所述系统还包括在化合物半导体层之上的背金属接触。
40.如权利要求30所述的系统，所述系统还包括在基底之上的透明导电层。
41.如权利要求30所述的系统，所述系统还包括在化合物半导体层之上的透明导电层。
42.如权利要求30所述的系统，所述系统还包括在化合物半导体层之上的第二化合物半导体层。
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