CN102044632A - 用于cigs电池的氧化锌膜方法和结构 - Google Patents

用于cigs电池的氧化锌膜方法和结构 Download PDF

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CN102044632A
CN102044632A CN2010105039601A CN201010503960A CN102044632A CN 102044632 A CN102044632 A CN 102044632A CN 2010105039601 A CN2010105039601 A CN 2010105039601A CN 201010503960 A CN201010503960 A CN 201010503960A CN 102044632 A CN102044632 A CN 102044632A
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zinc
zinc oxide
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罗伯特D·维廷
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Hetf Solar
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Abstract

本发明提供了用于CIGS电池的氧化锌膜方法和结构。本发明的用于制造薄膜光电器件的方法包括：提供包括吸收层和覆盖的窗口层的基板。将基板装载到室中并经受真空环境。真空环境处于从0.1托到约0.02托范围内的压力下。在一个具体实施方式中，将来源于二乙基锌物质、水物质的反应物物质和载气的混合物引入到室中。该方法进一步利用选择的流速将乙硼烷物质引入到反应物物质的混合物中。利用所述选择的流速形成氧化锌膜覆盖在窗口层之上以限定透明导电氧化物以提供约2.5毫欧-cm和更小的电阻率和约3000埃到5000埃的平均粒度。

Description

用于CIGS电池的氧化锌膜方法和结构
技术领域
本发明总体涉及光电材料及制造方法。更具体地，本发明提供了一种用于薄膜光电池的方法和结构。仅通过实例的方式，本发明的方法和结构提供了利用包含铜铟二硫化物物质的吸收材料的薄膜光电池。
背景技术
从一开始，人类已致力于发现开发能源的方式。能源来源于如石油化学、水力发电、原子核、风、生物质、太阳的形式，以及更原始的形式如木材和煤来源。在过去的世纪中，现代文明已依赖石油化学能量作为重要的能源。石油化学能源包括气体和油。气体包括较轻形式如丁烷和丙烷，通常用于加热住宅(取暖)和用作用于烹调的燃料。气体还包括汽油、柴油、和喷气燃料，通常用于运输目的。在一些地方，较重形式的石油化学品也可以用于加热住宅。不幸的是，石油化学燃料的供应是有限的，并且基于行星地球上可获的量基本上是固定的。另外，随着更多的人以增长的量利用石油产品，它将快速成为一种稀缺资源，其随时间将最终变得耗竭。
最近，已期望环境清洁和可再生的能源。清洁能源的实例是水力发电能。水力发电能来源于由水坝如内华达州的Hoover Dam产生的水流驱动的发电机。产生的电能用于为加利福尼亚洛杉矶的大部分城市供电。清洁和可再生的能源还包括风、波浪、生物质等。也就是说，风车将风能转化为更有用形式的能源如电能。清洁能源还有的其他类型包括太阳能。太阳能的具体细节可以在整个本发明背景中并更具体地在下文中找到。
太阳能技术通常将来自太阳的电磁辐射转化为其他有用的能量形式。这些其他能量形式包括热能和电能。对于电能应用，通常使用太阳能电池。虽然太阳能是环境清洁的并在每一点上已经是成功的，但是在其变为在全世界广泛使用之前仍然有许多限制有待解决。作为实例，一种类型的太阳能电池利用来源于半导体材料锭的结晶材料。这些结晶材料可以用于制造包括将电磁辐射转化为电能的光伏器件和光电二极管器件的光电器件。然而，结晶材料通常是昂贵的并难以大规模制备。另外，由这样的结晶材料制成的器件通常具有低能量转化效率。其他类型的太阳能电池使用“薄膜”技术以形成感光材料的薄膜用于将电磁辐射转化为电能。类似的限制存在于制造太阳能电池时薄膜技术的使用中。也就是说，效率通常较差。另外，膜可靠性通常较差并且在常规环境应用中不能用于较长的时期。通常，薄膜难以彼此机械地整合。这些常规技术的这些和其他限制可以在整个本发明说明书并更具体地在下文中找到。
根据上述，可以看出期望用于制造光电材料的改进的技术和得到的器件。
发明内容
根据本发明的实施方式，提供了一种用于形成光电池的方法和结构。更具体地，本发明提供了一种用于形成薄膜串联光电池的方法和结构。仅通过实例的方式，根据本发明的实施方式已经利用薄膜半导体材料实施。但是应当认识到根据本发明的实施方式可以具有更广泛范围的适用性。
在一个具体实施方式中，提供了一种用于制造薄膜光电池器件的方法。该方法包括提供基板。该基板包括吸收层和形成在吸收层上的覆盖(叠置)窗口层。该方法包括将基板装载到室中并使基板经受真空环境。在一个具体实施方式中，真空环境具有从0.1托到约0.02托范围内的压力。将来源于二乙基锌物质和水物质的反应物物质的混合物和载气引入到室中。该方法包括利用选择的流速将乙硼烷物质引入到反应物物质的混合物中。利用选择的流形成覆盖在窗口层之上的氧化锌(锌氧化物)膜以限定透明导电氧化物以提供约2.5毫欧-cm和更小的电阻率和约3000到5000埃的平均粒度。
在一个可替换的实施方式中，提供了一种用于形成薄膜光电器件的方法。该方法包括提供包括表面区的基板。该方法形成覆盖在表面区之上的第一电极层、以及形成覆盖在第一电极层之上的包含铜物质、铟物质、和硒化物物质的吸收材料。形成包含镉硒化物(硒化镉)物质的窗口层覆盖在吸收材料之上。在一个具体实施方式中，该方法利用一种或多种前体气体形成覆盖在窗口层之上的氧化锌层，该氧化锌层特征在于从约第一值到约第二值的范围的粒度。在一个具体实施方式中，一种或多种前体气体包括锌物质和氧物质以及载气。在一个具体实施方式中，载气包括至少氮物质。该方法在大于约200摄氏度的温度下进行至少形成氧化锌层的全部或一部分，同时保持包含锌物质和氧物质的气体混合物的选择的流速。
通过根据本发明的实施方式，可以获得许多益处。例如，可以利用对常规设备没有实质改变的技术制造薄膜串联光电池。另外，本发明的薄膜光电池与常规的光电池相比具有提高的转换效率，并提供了一种将阳光转换为电能的节约成本的方式。取决于实施方式，可以获得一个或多个这些益处。通过整个本发明说明书以及特别是下面的内容更详细地描述了这些和其他益处。
附图说明
图1为示出了根据本发明一个实施方式的制造薄膜光电器件的方法的简化工艺流程图。
图2-6为示出了根据本发明实施方式的制造薄膜光电器件的方法的简化图。
具体实施方式
根据本发明的实施方式，提供了用于形成光电池的方法和结构。更具体地，根据本发明的实施方式提供了用于形成薄膜光电池的方法和结构。仅仅通过实例的方式，根据本发明的实施方式已经利用薄膜半导体材料实施。但是应当认识到，根据本发明的实施方式可以具有更广泛范围的适用性。
图1为示出了根据本发明一个实施方式的形成光电池的方法的简化工艺流程图。如所示的，该方法起始于开始步骤(步骤102)。提供了透明的基板。在一个具体实施方式中，透明基板可以使用玻璃基板如钠钙玻璃。也可以使用其他透明基板材料。这些其他透明基板材料可以包括熔融石英(石英玻璃)、石英等。形成第一电极层覆盖在透明基板的第一表面区之上(步骤106)。在一个具体实施方式中，可以利用钼材料提供第一电极层。根据应用，也可以使用其他电极材料如透明导电氧化物材料、其他金属材料。该方法包括形成覆盖在第一电极层之上的吸收层(步骤108)、以及形成覆盖在吸收层之上的窗口层(步骤110)。在一个具体实施方式中，吸收层包含CIGS材料或CIS材料，窗口层包含镉硫化物材料。在一个具体实施方式中，该方法包括将具有形成在基板上的吸收层和窗口层的基板(包括透明基板)装载到室中(步骤112)。该方法使基板经受真空环境(步骤114)并引入来源于含锌的物质和水物质的反应物物质的混合物和载气(步骤116)。在一个具体实施方式中，含锌的物质可以由二乙基锌提供。在一个具体实施方式中，该方法利用选择的流速将乙硼烷物质引入反应物物质的混合物中。在一个具体实施方式中，形成包含氧化锌材料的透明导电氧化物材料(步骤118)覆盖在窗口层之上。该方法进行其他步骤(步骤120)以完成光电池。该方法终止于结束(END)步骤(步骤122)。当然，可以存在其他改变、更改、和替换。
其中，所述二乙基锌物质可以为二乙基锌蒸气，所述水物质可以为水蒸气。其中，所述载气包括氮气或氩气。
上面的步骤顺序提供了一种根据本发明实施方式的形成光电器件的方法。如所示的，在一个具体实施方式中，该方法包括形成包含氧化锌材料的透明导电氧化物层的步骤。氧化物材料优选特征在于大于约99％的透光率和约2.5毫欧-cm和更小的电阻率。取决于实施方式，可以加入一个或多个步骤，可以去除一个或多个步骤，以及可以以不同的顺序进行一个或多个步骤而不偏离本文的权利要求的范围。本领域技术人员应当认识到其他改变、更改、和替换。
图2-6为示出了根据本发明实施方式的形成薄膜光电器件的方法的简图。这些图仅是实例，不应当不适当地限制本文的权利要求。本领域技术人员会认识到其他改变、更改、和替换。如图2中所示，提供了包括表面区204的透明基板构件202。在某一个实施方式中，基板构件可以为玻璃材料如钠钙玻璃。钠钙玻璃为用于透明基板构件的节约成本的选择。也可以使用其他合适的透明基板如石英、熔融石英、太阳能玻璃(solar glass)。每个透明基板可以包括沉积在表面区上的阻挡层。在一个具体实施方式中，阻挡层可以防止钠离子从玻璃材料扩散到光电材料区中。阻挡层可以为利用以下技术沉积的介电材料如硅氧化物(氧化硅)，如溅射工艺、化学气相沉积工艺、包括等离子体增强工艺等。也可以使用其他阻挡材料。取决于实施方式，这些阻挡材料包括氧化铝、氮化钛、氮化硅、氧化钽、氧化锆。
参照图3，该方法包括形成覆盖在透明基板构件的表面区之上的第一电极层302，该透明基板构件可以具有形成在其上的阻挡层。可以利用透明导电氧化物(TCO)如氧化铟锡(通常称为ITO)、掺杂氟的锡氧化物等提供第一电极层。在一些实施方式中，可以利用金属材料提供第一电极层。在一个具体实施方式中，金属材料可以为钼材料。可以利用沉积技术如溅射、电镀、物理气相沉积(包括蒸发、升华)、化学气相沉积(包括等离子体增强工艺)，接着进行图案化工艺来形成钼材料。钼材料对基于CIG或CIGS的薄膜光电池提供了优于其他电极材料的一些优势。例如，钼材料提供了对于CIGS膜来说低的接触电阻和在随后的工艺步骤中的稳定性。在一个具体实施方式中，通过沉积第一钼层覆盖在透明基板构件之上来形成钼材料。在一个具体实施方式中，第一钼层具有第一厚度和抗拉特性。形成具有压缩特征和第二厚度的第二钼层覆盖在第一钼层之上。在一个具体实施方式中，如所示的，可以进一步图案化包含钼材料的第一电极层。钼材料的沉积和图案化的进一步的细节可以至少在共同转让的于2008年9月30日提交的美国临时申请号61/101,646(代理人档案号：026335-003800US)和于2008年9月30日提交的美国临时申请号61/101,650(代理人档案号：026335-003900US)中找到，将其通过引用的方式并入本文中。当然，可以存在其他改变、更改、和替换。
如图4所示，该方法包括形成覆盖在第一电极层的表面区之上的吸收层402。在一个具体实施方式中，吸收层可以为薄膜半导体材料。在一个具体实施方式中，取决于应用，薄膜半导体材料为由铜铟二硫化物材料、或铜铟镓二硫化物材料、或铜铟二硒化物材料、或铜铟镓二硒化物材料、这些的任何组合等提供的p型半导体材料。典型地，p型特征可以利用掺杂剂如硼或铝物质提供。吸收层可以通过如溅射、电镀、蒸发(包括硫化或硒化步骤)的技术沉积。形成吸收材料的进一步的细节可以在共同转让的标题为“HighEfficiency Photovoltaic Cell and Manufacturing Method”的临时美国专利申请号61/059,253中找到，将其通过引用的方式并入本文中。
在一个具体实施方式中，该方法形成覆盖在吸收层的表面区之上的窗口层502以形成光电膜堆叠从而为光电池提供pn结。在一个具体实施方式中，通常利用用于p型吸收层的广带隙n型半导体材料来提供窗口层。在一个优选的实施方式中，对于利用CIGS、CIS和相关材料作为吸收层的光电池，窗口层利用镉硫化物材料。窗口层可以利用如溅射、真空蒸发、化学浴沉积等的技术来沉积。
参照图6，该方法包括提供基板602。该基板包括透明基板构件，该透明基板构件具有覆盖在透明基板构件之上的第一电极层。薄膜吸收层覆盖在第一电极层之上，而窗口层覆盖在薄膜吸收层之上。如所示的，将基板装载到室604中。该室包括内容积606。该室还包括泵送系统608以提供合适的真空水平。如所示的，在一个具体实施方式中，该室包括一个或多个气体管线610和多个辅助件以引入一种或多种前体物质用于形成覆盖在窗口层之上的透明导电氧化物材料614。该室包括一个或多个加热装置612以提供用于透明导电材料沉积的的合适的反应温度。在一个优选的实施方式中，透明导电氧化物包括氧化锌材料。当然，可以存在其他改变、更改、和替换。
再次参照图6，该方法包括将基板装载到室中。在一个具体实施方式中，向下抽吸该室与基板以使压力在从约0.1托到约0.02托的范围。利用一个或多个气体管线，将反应物或前体物质的混合物引入到室中。在一个具体实施方式中，对于氧化锌材料，反应物物质的混合物可以包括利用载气提供的二乙基锌材料和含氧的物质。在一个具体实施方式中，含氧的物质可以为水。取决于实施方式，二乙基锌材料可以以半导体级、或催化剂级提供。在一个具体实施方式中，水与二乙基锌比率大于约1到约4。在另一个实施方式中，水与二乙基锌比率为约1。在一个具体实施方式中，载气可以为惰性气体如氮、氩、氦等。在某一个实施方式中，来源于乙硼烷物质的含硼的物质也可以以选择的流速与反应物的混合物一起引入以形成掺杂硼的氧化锌材料。取决于应用，也可以使用其他含硼的物质如硼卤化物(例如，三氯化硼、三氟化硼、三溴化硼)、或硼氢卤化物。可以以0％至约5％的乙硼烷与二乙基锌比率提供乙硼烷物质。在一个具体实施方式中，乙硼烷比率与二乙基锌比率为约1％。取决于实施方式，在氧化锌材料沉积期间，该室可以处于约0.5托到约1托的压力下。在一个具体实施方式中，为了氧化锌材料的沉积，将基板保持在从约130摄氏度到约190摄氏度范围内的温度。在一个可替换的实施方式中，可以将基板保持在约200摄氏度的温度，并且可以更高。含硼的物质可以降低氧化锌材料的电阻率特性。取决于氧化锌材料中含硼的物质的水平，氧化锌材料可以具有约2.5毫欧-cm和更小的电阻率。此外，取决于含硼的物质的水平，氧化锌材料可以具有从约3000埃到约5000埃范围内的粒度以对于在从约800纳米到约1200纳米范围内的波长范围中的电磁辐射提供80％或更大并优选为90％和更大的透射比。在一个具体实施方式中，氧化锌材料可以具有模糊的(hazy)外观。当然，可以存在其他改变、更改、和替换。
虽然已经利用具体的实施方式描述了本发明，但应当理解可以实施对本发明中所用的方法的多种改变、更改、和变换而没有偏离如所附的权利要求中限定的本发明的精神和范围。例如，可以利用硼作为掺杂剂物质示出氧化锌材料。也可以使用其他掺杂剂如氢、铝、铟、镓等。此外，虽然上面已经就CIS和/或CIGS薄膜电池的具体结构进行了一般描述，但也可以使用其他具体CIS和/或CIGS构造，如在美国专利号4,612,411和美国专利号4,611,091中提及的那些构造，将其通过引用方式并入本文中，而没有偏离通过本文的权利要求描述的本发明。此外，根据本发明的实施方式可以用于其他薄膜构造如由金属氧化物材料、金属硫化物材料或金属硒化物材料提供的那些构造。本领域的普通技术人员会认识到其他改变、更改、和替换。

Claims (23)

1.一种用于制造薄膜光电器件的方法，所述方法包括：
提供包括吸收层和覆盖的窗口层的基板；
将所述基板装载到室中；
使所述基板经受从0.1托到约0.02托范围内的真空环境；
引入来源于二乙基锌物质和水物质的反应物物质的混合物和载气；
利用选择的流速将乙硼烷物质引入到所述反应物物质的混合物中；
利用所述选择的流速形成覆盖在所述窗口层之上的氧化锌膜以限定透明导电氧化物以提供约2.5毫欧-cm和更小的电阻率和约3000埃到约5000埃的平均粒度。
2.根据权利要求1所述的方法，其中，所述二乙基锌物质为二乙基锌蒸气。
3.根据权利要求1所述的方法，其中，所述水物质为水蒸气。
4.根据权利要求1所述的方法，其中，所述载气包括氮气或氩气。
5.根据权利要求1所述的方法，其中，所述水与二乙基锌比率为大于约1到约4
6.根据权利要求1所述的方法，其中，所述水与二乙基锌比率为约1。
7.根据权利要求1所述的方法，其中，所述乙硼烷与二乙基锌比率从约0％到约5％的范围。
8.根据权利要求1所述的方法，其中，所述乙硼烷与二乙基锌比率为1％。
9.根据权利要求1所述的方法，其中，将所述基板保持在约130摄氏度到约190摄氏度的温度。
10.根据权利要求1所述的方法，其中，将所述基板保持在大于约200摄氏度的温度。
11.根据权利要求1所述的方法，其中，所述氧化锌膜是模糊的。
12.根据权利要求1所述的方法，其中，所述氧化锌膜具有90％和更大的透光比。
13.根据权利要求1所述的方法，其中，所述氧化锌膜对于具有约800纳米到约1200纳米的波长的电磁辐射具有80％和更大的透射比。
14.根据权利要求1所述的方法，其中，所述引入将所述室的压力增大到约0.5到1托。
15.根据权利要求1所述的方法，其中，所述二乙基锌为半导体级。
16.根据权利要求1所述的方法，其中，所述二乙基锌为催化剂级。
17.根据权利要求1所述的方法，其中，所述吸收层包含CIGS材料或CIG材料。
18.根据权利要求1所述的方法，其中，所述窗口层包含镉硫化物材料。
19.一种用于形成薄膜光电器件的方法，所述方法包括：
提供包括表面区的基板；
形成覆盖在所述表面区之上的第一电极层；
形成覆盖在所述第一电极层之上的包含铜物质、铟物质、和硒化物物质的吸收材料；
形成覆盖在所述吸收材料之上的包含镉硒化物物质的窗口层；
利用包含锌物质和氧物质的一种或多种前体气体和包含至少氮物质的载气形成覆盖在所述窗口层之上的氧化锌层，所述氧化锌层的特征在于从约3000埃到约5000埃范围内的粒度；以及
在大于约200摄氏度的温度下进行至少形成氧化锌层的全部或一部分，同时保持包含锌物质和氧物质的气体混合物的选择的流速。
20.根据权利要求19所述的方法，其中，含氧的物质来源于水蒸气。
21.根据权利要求19所述的方法，其中，所述锌物质来源于二乙基锌。
22.根据权利要求19所述的方法，其中，所述氮物质为氮气。
23.根据权利要求19所述的方法，其中，所述氧化锌层的特征在于99％和更大的透光比。
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