CN102544213A - 制造硫化镉层的方法 - Google Patents

制造硫化镉层的方法 Download PDF

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CN102544213A
CN102544213A CN2011104619182A CN201110461918A CN102544213A CN 102544213 A CN102544213 A CN 102544213A CN 2011104619182 A CN2011104619182 A CN 2011104619182A CN 201110461918 A CN201110461918 A CN 201110461918A CN 102544213 A CN102544213 A CN 102544213A
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B·A·科列瓦尔
S·费尔德曼-皮博迪
R·D·戈斯曼
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Abstract

提供了一种用于制造硫化镉层的方法。该方法包括多个步骤，所述步骤包括提供衬底以及在衬底上设置含镉层，随后硫化含镉层。

Description

制造硫化镉层的方法
技术领域
本发明主要涉及一种制造硫化镉的方法。具体地，本发明涉及制造例如用在光伏电池或太阳能电池中的硫化镉层的方法。
背景技术
太阳能在世界许多地方全年是充沛的。不幸的是，可利用的太阳能通常无法有效地用于生产电能。例如，典型的太阳能电池达到的转化效率低于约20％。传统光伏电池以及由这些电池产生电的成本通常是很高的。此外，光伏电池通常包括形成在衬底上的多个层，并因此太阳能电池的制造通常要求大量的工艺处理步骤。结果，工艺处理步骤、层、界面的高数量以及复杂性增大了制造这些电池需要的时间和资金量。研究者持续地努力提高光伏(PV)电池的效率并降低其制造成本。
典型的多晶薄膜PV电池具有被称做“窗口”层的非常薄(小于0.1微米)的层。窗口层的作用在于与吸收层组合形成异质结。窗口层需要足够薄并具有足够宽的带隙(2.4eV或更大)以便使得大多数可利用的光穿过以到达吸收层。对于CIGS和CdTe型太阳能电池而言，用于窗口层最常见材料为硫化镉(CdS)。硫化镉是直接带隙半导体并具有许多其它应用，例如用在光检测器和光电阻中。
已有多种方法用于沉积CdS薄膜，例如化学浴沉积、溶胶-凝胶、电化学沉积、热蒸发、溅射和喷涂。但是，大多数的这些方法异常昂贵和/或复杂并因此无法用于以合理成本大规模制造薄膜。
因此，需要一种更有效和更廉价的用于大规模生产的制造硫化镉薄膜的方法。
发明内容
本发明的实施方案涉及一种用于制造硫化镉层的方法。
依照本发明的一个实施方案，该方法包括多个步骤，所述步骤包括提供衬底以及在衬底上设置包含镉的层。随后硫化该包含镉的层以基本将镉转换为硫化镉。
附图说明
参照附图阅读以下详细说明，能更加明晰本发明的这些和其它特征、方面以及优点，其中：
图1显示了依照本发明一例示性实施方案的光伏装置的示意图；
图2显示了依照本发明另一例示性实施方案的光伏装置的示意图；
图3显示了依照本发明一些实施方案的制造硫化镉层的方法的流程图；
图4显示了依照本发明一例示性实施方案的制造硫化镉层的方法的流程图；
图5显示了依照本发明另一例示性实施方案的制造硫化镉层的方法的流程图；
图6显示了依照本发明一些实施方案的适用于溅射沉积的腔室的示意性截面图。
详细说明
如在本文说明书和权利要求书中全篇使用的近似用语，在不导致其涉及的基本功能发生改变的情况下，可用于修饰可容许改变的任何数量表示值。因此，借由例如为“约”的术语(一或多个)修饰的数值并不限于特定的精确数值。某些情况下，近似用语可相应于用于测量数值的仪器的精度。
在以下说明书和权利要求中，单数形式“一”、“一个”、“该”包括复数的所指物，除非上下文明确地以其它方式指出。术语“包括”、“包含”、“具有”意在包含的且意味着除了所列出元件外可存在额外元件。此外，“顶”、“底”、“上”、“下”和这些术语的变体为便利性而使用，但不要求组件的任何特定定位，除非以其它方式陈述。如在此所用，术语“沉积在......上”或“沉积在......上方”既指直接接触地也指在其间具有中间层的间接地固定或设置。
如在此所用，术语“可”和“可为”表示在一组情况范围内发生的可能性；具有特定特性、特征或功能；和/或通过表示与所限定动词相关的能力、性能或可能性中的一个或多个来限定另一动词。因此，“可”和“可为”的使用表示修饰术语是明显地恰当的、有能力的或合适的用于所表示的能力、功能或用途，尽管考虑到所修饰术语在某些情况下可能并非是恰当的、有能力的或合适的。例如，某些情况下，可以预期事件或能力，尽管在其它情况下事件或能力无法发生-这种区别通过术语“可”和“可为”来表示。
术语“透明”，如在此所用，意味着材料允许大部分入射太阳辐射穿过。大部分可为入射太阳辐射的至少约80％。
通常地，在此出于简短讨论目的，包括作为吸收层的碲化镉(CdTe)的光伏(PV)电池可称做“CdTe PV电池”且那些包括Cu(In，Ga，Al)(Se，S)2(CIGS)的光伏(PV)电池可被称做“CIGS PV电池”。PV电池的其它示例可包括铜-锌-锡-硫化物(CZTS)PV电池和金属硫化物PV电池。
光伏电池通常包括衬底、透明电极、CdS窗口层、吸收层以及基电极。图1显示了包括透明衬底12的CdTe PV电池10。衬底12包括形成透明电极的透明导电层14。CdS窗口层16被沉积在透明导电层14上，随后是吸收层18。
透明导电层14(当该层包括氧化物时，也被称做TCO层)设置在衬底12的表面上。适用于透明导电层14的材料可包括氧化物、硫化物、磷化物、碲化物或其组合。这些透明导电材料可被掺杂或不掺杂。在例示性实施方案中，透明导电层14可包括氧化物，例如二氧化钛、氧化硅、氧化锌、氧化锡、掺铝氧化锌、掺氟氧化锡、锡酸镉(氧化镉锡)或锡酸锌(氧化锌锡)。在另一实施方案中，透明导电层14包括一种或多种含铟氧化物。合适的含铟氧化物的一些示例为氧化铟锡(ITO)、Ga-In-Sn-O、Zn-In-Sn-O、Ga-In-O、Zn-In-O及其组合。合适的磷化物可包括磷化铟、磷化镓等等。
具有比透明导电层14更高薄膜电阻的任选的第二透明导电层15可设置在透明导电层14上方。第二透明导电层15被称为高电阻透明(HRT)层或高电阻透明导电层。未掺杂的锡酸锌(ZnSnO4)、氧化锌(ZnO)和氧化锡(SnO2)可被用作HRT层。与没有HRT的可行技术相比，HRT层通常允许在光伏电池中使用更薄的CdS窗口层，因此提高了在蓝区内电池的量子效率。HRT层也可通过形成阻止不需要的物质从衬底12扩散的阻挡层以及与CdS窗口层16的前接触来提高电池效率。
图2显示了CIGS PV电池或铜-锌-锡-硫化物(CZTS)PV电池的例示性实施方案。电池20包括可不透明的衬底22。不透明层24被设置在衬底22上以形成吸收层，且CdS窗口层26沉积在不透明层24上方。透明导电层28可被设置在窗口层26上。在这些例子中，不透明层24包括选自铜、银、铟、镓、铝、锌、锡和硒的一种或多种元素。在特定实施方案中，不透明层包括铜。
光敏材料通常用于形成吸收层。合适的光敏材料的示例可包括碲化镉(CdTe)、Cu(In，Ga，Al)(Se，S)2(CIGS)和铜-锌-锡-硫化物(CZTS)。在某些情况下，这些材料可进一步被一种或多种另外的元素所替代。
有多种方法沉积CdS薄膜。一种生产CdS膜的方法是通过喷涂镉盐和可溶硫化物的溶液。硫化镉因此通过在衬底上原位的双分解反应而形成。例如可参见美国专利4159914。另一种喷涂技术包括镉氧化膜的化学喷涂沉积，随后采用硫化氢处理氧化膜，反应形成硫化镉。例如可参见美国专利4242374。通过喷涂沉积并热分解可溶性镉盐来得到氧化镉膜，可溶性镉盐例如硝酸镉、草酸镉或醋酸镉。这些工艺步骤复杂且难以控制。双分解缩合或两种化学物原位的类似反应(其用以产生一种或多种不同化学物)，取决于化学物的相对比例、浓度、反应温度以及反应时间。
此外，最常用的生产CdS薄膜的方法是从CdS靶溅射，这是极其昂贵的材料。溅射是已知的且广泛使用的用于有效率和大规模涂覆的技术。但是，从CdS靶溅射速度缓慢且材料成本昂贵。
在此所述的本发明实施方案提供了一种克服了本领域状态所述缺陷的替代方法。依照本发明一个实施方案，该制造硫化镉层的方法包括按照图3流程图40所示的依次步骤。步骤42提供衬底。衬底的选择取决于所需的应用，例如PV电池类型。
合适的衬底材料的示例可包括但不限于玻璃、半导体、掺杂半导体、非晶介质、晶体介质、金属、聚合物及其组合。特定实施方案中，衬底为玻璃板。其它特定实施方案中，衬底为柔性聚酰亚胺。又一实施方案中，衬底包括金属。
在某些实施方案中，衬底具有基本平坦表面。如在此所用，“基本平坦表面”通常涉及基本平直表面。表面可以是平滑的，尽管其可包括相对较小程度的纹理、凹痕和各种不规则(例如小于约1微米的RMS粗糙度，或更具体地小于约300nm)。
方法40进一步包括在衬底上设置含镉层的步骤44。特定实施方案中，该层包括镉金属。某些实施方案中，含镉层被沉积在透明导电层14上方，如图1所示和图4流程图所述。这些情况下，如果采用HRT层，含镉层被沉积在HRT层15上方。某些其它实施方案中，含镉层被沉积在不透明层24上方，如图2所示和图5的流程图所述。
多种薄膜沉积技术可被用于沉积含镉层，例如化学浴沉积、溶胶-凝胶、电化学沉积、热蒸发、溅射和喷涂。依照本发明某些实施方案，真空沉积技术被用于获得高质量膜。真空沉积技术的非限定性示例包括蒸发沉积、电子束物理气相沉积、溅射沉积、阴极电弧沉积或脉冲激光沉积。特定实施方案中，溅射是用于在大面积上以简单和可控方法沉积高质量膜的适宜的沉积技术。
图6显示了溅射系统50的示例。溅射系统50通常包括真空腔室52。溅射源56被连接至电源54并包括用于溅射操作的溅射枪和靶(未示出)。电源54可为直流(DC)电源、射频(RF)电源、双极脉冲直流电源、高能脉冲直流电源或其任意组合。溅射源56被安装在延伸进入真空腔室52的支柱58上。依照本发明一个实施方案，靶包括镉金属。
溅射系统50采用具有重离子例如氩的气体氛围。衬底支架60支撑衬底62，衬底62通常以适于膜生长的方向和距离被固定。衬底62可被加热。为了沉积镉金属层，衬底62被放置在腔室52内约10至约90分钟，这取决于层所需厚度。
所需的硫化镉(CdS)层的厚度通常需要在PV电池中最小化以获得高效率。某些实施方案中，含镉层厚度可在约10纳米至约200纳米之间，部分地取决于溅射时间。特定实施方案中，层的厚度范围从约50纳米至约100纳米。某些实施方案中，可使用具有多个溅射源的直列式(in-line)系统来沉积镉金属。
方法40进一步提供步骤46，用于含镉层的硫化。如在此所用，“硫化”涉及将含镉层暴露在含硫氛围中以将镉基本转化为硫化镉。一个实施方案中，含硫氛围包括含硫气体。含硫气体的合适示例包括但不限于硫化氢、二硫化碳、六氟化硫(SF6)、二氯化硫、烷硫醇和硫醚。其它示例可包括有机金属前驱物，尽管这些物质可在工艺处理之后留下不希望的有机残留物。
此外，硫化发生在低于所形成的硫化物分解或升华的温度下。因此，在约100摄氏度至约1000摄氏度的温度范围内执行含镉层的硫化。特定情况下，硫化温度范围从约200摄氏度至约500摄氏度。含镉层转变为硫化镉层部分取决于层的厚度、硫化时间以及所选温度。某些实施方案中，含镉层的硫化执行时间段从约2分钟至约5小时，且在特定实施方案中，约5分钟至约30分钟。
选择硫化时间和硫化温度以将含镉层中至少约50％的镉转化为硫化镉(CdS)。某些实施方案中，至少约80％的镉，且某些实施方案中，基本所有的镉被转化为硫化镉。
一个实施方案中，含镉层的硫化可在层沉积之后在真空腔室内进行，例如为了避免镉的氧化。但是，另一实施方案中，含镉层的硫化可在真空腔室外实施，例如为了避免污染真空腔室。沉积之后，含镉层可被转移至真空腔室的另一区域或地带以执行硫化。
某些实施方案中，例如在CIGS或CZTS PV电池中，含镉层被设置在不透明层上。这些情况下，不透明层和含镉层同时均被硫化以分别形成光敏材料层和硫化镉层。
某些实施方案中，硫化之后，特定含量的氧可被混入含镉层中以形成CdS∶O膜。这些特定情况下，含镉层中的氧含量通常大于约1原子百分比并小于约50原子百分比。特定实施方案中，氧含量可在约1原子百分比和约45原子百分比之间变化，且更具体地，在约2原子百分比和约20原子百分比之间。
与当前可利用的方法相比，上述方法有利地提供了一种相对经济的工艺来沉积硫化镉层。该方法在成本和时间上均相对较经济。与溅射金属镉相比，溅射硫化镉(CdS)由于其缓慢的生长速度是困难的且耗时的。此外，CdS靶与金属镉靶相比相对昂贵。本发明方法因此与传统CdS沉积相比节省了时间和材料成本。
上述制造硫化镉层的工艺/方法可非常容易地应用于工业生产线。
尽管仅在此显示并描述了本发明的特定特征，对于本领域技术人员而言，可发生许多修改和改变。因此，需要知晓的是，所附权利要求意在覆盖落入本发明真实精神内的所有修改和改变。
元件列表
10CdTe PV电池
12透明衬底
14透明导电层
15任选的第二透明导电层
16CdS窗口层
18吸收层
20CIGS PV电池
22衬底
24不透明层
26CdS窗口层
28透明导电层
40流程图
42提供衬底的步骤
44在衬底上设置含镉层的步骤
50溅射系统
52真空腔室
54电源
56溅射源
58支柱
60衬底支架
62衬底

Claims (10)

1.一种用于制造硫化镉层的方法，该方法包括步骤：
提供衬底；
在衬底上设置包含镉的层以形成含镉层；以及
硫化该含镉层以基本将镉转化为硫化镉以形成硫化镉层。
2.权利要求1的方法，其中，衬底包括设置在衬底表面上的透明导电层。
3.权利要求2的方法，其中，衬底进一步包括设置在透明导电层上的高电阻透明(HRT)层。
4.权利要求2的方法，其中，含镉层被沉积在透明导电层上。
5.权利要求1的方法，其中，衬底包括不透明层，所述不透明层包括选自铜、银、铟、镓、铝、锌、锡和硒的一种或多种元素。
6.权利要求5的方法，其中，含镉层被设置在不透明层上。
7.权利要求1的方法，其中硫化含镉层包括将含镉层暴露于含硫氛围。
8.权利要求7的方法，其中，含硫氛围包括选自硫化氢、二硫化碳、六氟化硫、二氯化硫、烷硫醇和硫醚的气体。
9.权利要求7的方法，其中，含镉层的硫化在从约100摄氏度至约1000摄氏度的温度范围内执行。
10.权利要求7的方法，其中，含镉层的硫化执行约2分钟至约5小时的时间段。
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