CN101094726A - 用于以cigs建立原位结层的热方法 - Google Patents

用于以cigs建立原位结层的热方法 Download PDF

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CN101094726A
CN101094726A CNA200580045415XA CN200580045415A CN101094726A CN 101094726 A CN101094726 A CN 101094726A CN A200580045415X A CNA200580045415X A CN A200580045415XA CN 200580045415 A CN200580045415 A CN 200580045415A CN 101094726 A CN101094726 A CN 101094726A
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约翰·R·塔特尔
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Abstract

本发明大体上涉及光电元件的领域，且更具体地说，涉及使用热方法制造薄膜太阳能电池。具体地说，揭示一种用以通过原位结形成工艺来制造CIGS太阳能电池的方法。

Description

用于以CIGS建立原位结层的热方法
相关申请案的交叉参考
本申请案主张2004年11月10日申请的第60/626,843号美国临时专利申请案的优先权。
技术领域
本文所揭示的发明大体上涉及光电元件领域，且更具体地说，涉及使用原位结方法来建立薄膜太阳能电池。
背景技术
能在实验室中制造相对有效的光电(“PV”)电池；然而，已证实难以在商业上用对于商业生存性较关键的一致重复性和效率来扩大这些方法的规模。缺少有效的薄膜制造方法已导致PV电池不能有效取代市场上的传统能量来源。从实验室批量处理方法转变为既较便宜又较好控制的有效工业过程将帮助PV技术向主流市场前进。
在没有有效的薄膜制造方法的情况下，PV电池不能有效地取代当前能量来源。为制造PV电池，在支撑层(例如玻璃、金属或塑料箔)上沉积PV材料的薄半导体层。由于薄膜直接带隙半导体材料比间接带隙结晶半导体材料具有更高的光吸收性，因而在极薄的原子、分子或离子连续层中沉积PV材料。基本光电堆叠设计示范说明PV电池的典型结构。在所述设计中，电池包含衬底、障壁层、背接触层、半导体层、碱性材料、n型结缓冲层、本征透明氧化层和导电透明氧化层。
二硒化铜铟(CIS)(其中镓可取代所有或部分铟(CIGS)和/或硫可取代所有或部分硒(CISS))的化合物最有希望用于薄膜太阳能电池中的吸收体层中。与其它吸收体层化合物相比，CIGS电池已表明最高效率和良好稳定性。通常，通过基于真空的技术来沉积CIGS膜。然而，包含PV装置的多个层向大规模生产系统提出挑战。目前，不存在用于连续生产CIGS装置的可靠技术。另外，典型的PV电池制造技术涉及必须需要接触人工、高资金成本和低制造输出的批量处理。相反地，连续方法可最小化资金成本和接触人工，且同时最大化产品生产率和产量。
明确地说，CIGS系统对制造商构成独特挑战。如2002年10月14日Ramanathan等人论述的，用于大面积模块制造的方法涉及沉积金属前体堆叠和随后在硒和硫周围环境中形成化合物。在光电应用中，p型CIGS层与n型CdS层进行组合，以形成p-n异质结CdS/CIGS装置。然而，此过程是有问题的。CdS层的带隙仍然低到足以限制太阳光谱中能到达吸收体的短波长部分，且这导致减少可收集的电流。此减少对于较高带隙CIGS电池变得相应较严重。此外，此过程造成有害废料，对废料的处置对于可能的制造来说是一项挑战。因此，此项技术中需要寻找化学浴沉积(“CBD”)CdS过程的实用替代方案。
尽管已提议针对CBD CdS过程的某些替代方案，但在大规模连续制造的情形下没有一个替代方案是可行选项。这些替代方案中的某些方案包括添加由以下各物组成的层：ZnS、ZnO、Zn(S，O)、ZnSe、In2S3和In(OH)xSy。然而，插入这些替代缓冲层通常涉及更多化学步骤以及后沉积退火或光浸渍以变得完全有效。添加这些后沉积步骤降低了制造过程的效率，且使得产品遭受潜在的错误处理和污染。因此，此项技术中需要一种用于制造薄膜太阳能电池的方法，其使用CBD CdS技术的替代方案来插入缓冲层，而不需要额外化学步骤。
发明内容
本发明涉及用于制造光电装置的新方法和由所述方法制得的光电装置。
在优选实施例中，n型层经形成为处理的延续，藉此CIGS在小于460℃的升高温度下暴露于In、Ga和Se的活动。在此类实施例中，In、Ga和Se的活动大体上不变化，但衬底温度有意地降低或由于从较高温度的自然冷却而降低到In、Ga和Se的活动不再与CIGS吸收体层反应的那一点。代替地，这些元素沉积并形成其自身的具有(In，Ga)ySen型层形式的化合物，所述化合物充当结补伴和充当位于CIGS与随后本征ZnO层之间的缓冲体。本征透明氧化层支撑透明导电氧化层和顶部金属栅格。
附图说明
图1相对于光电堆叠设计的沉积来展示根据本发明的薄膜太阳能电池的实施例，其中吸收体层是CIGS且结缓冲层通过本发明方法形成。
具体实施方式
二硒化铜铟(CuInSe2)和二硒化铜铟镓(CuIn1-xGaxSe2)的黄铜三重薄膜在近些年来已成为半导体装置的大量关注和研究的主题，其中所述CuInSe2和CuIn1-xGaxSe2两者一般被称为Cu(In，Ga)Se2或CIGS。硫也能(且有时)用以取代硒，所以所述化合物有时也甚至更一般地被称为Cu(In，Ga)(Se，S)2，以便包含所有这些可能组合。这些装置根据其组成元素的群组也被称为I-III-VI2装置。这些装置对于光电装置或太阳能电池吸收体应用而受到特别关注。对于光电应用，p型CIGS层与n型CdS层组合，以形成p-n异质结CIGS/CdS装置。
CIGS的直接能隙导致较大光学吸收系数，所述较大光学吸收系数又允许使用大约1-2μm的薄层。CIGS装置的额外优势是其长期稳定性。
观看图1，所有层均沉积在衬底105上，所述衬底105可包含多种功能材料中的一种，例如玻璃、金属、陶瓷或塑料。预期衬底厚度可在大约10.0μm-10mm的范围内，且可为刚性的或柔性的。优选地，衬底充当用于互连的背接触件。
直接沉积在衬底105上的是障壁层110。所述障壁层110包含薄导体或非常薄的绝缘材料，且用以阻断不良元素或化合物从衬底向外扩散到电池的其余部分。此障壁层110可包含铬、钛、二氧化硅、氮化钛和具有必要导电性和耐久性的相关材料。优选具有较薄障壁层110。
下一沉积层是背接触层120，其包含非反应性金属(例如钼)。所述背接触层是用于太阳能电池的电接触件。所述层可进一步用以防止化学化合物从其它层扩散到太阳能电池结构。所述层还充当衬底105与太阳能电池结构之间的热膨胀缓冲体。
下一层沉积在所述背接触层120上，且是p型半导体层130，以改进吸收体与背接触件之间的粘附性。所述p型半导体层130可为I-IIIa，b-VI同型半导体，但优选的成份为Cu:Ga:Se、Cu:Al:Se或Cu:In:Se与前述化合物中的任一者的合金。
在此实施例中，p型吸收体层155的形成涉及多个离散层的相互扩散。最终如图1中所示，p型半导体层130和150组合成单个复合层155，其充当太阳能的主要吸收体。在此实施例中，添加碱性材料140以用于给后续层的生长播种，以及增加吸收体层155的载流子浓度和晶粒大小，借此增加PV电池的转换效率。
仍参看图1，下一层包含另一半导体层150(也称为CIGS吸收体层)。所述层150可包含一种或多种化合物，所述化合物包括类型I元素(例如Cu或Ag)和/或类型III元素(例如In、Ga或Al)和/或类型VI元素(例如Se和/或S)。优选地，p型层150包含I-(IIIa，IIIb)-VI2层(IIIa＝In，IIIb＝Ga，Al)，其中0.0＜IIIb/(IIIa+IIIb)＜0.4。优选地，p型吸收体层包含CuIn1-x:Gax:Se2，其中x在0.2到0.3之间的范围内，其中厚度在约1μm到约3μm的范围内。
通过在碱性材料140上方传递I、III和VI前体材料或经反应的I-III-VI化合物来形成半导体层150。半导体层可形成为混合物或一系列薄层。
在替代实施例中，半导体层可由分级的吸收体层组成，所述吸收体层包含溅镀目标前体的各种组合的多个层。举例来说，Cu2Se:Ga2Se3:In2Se3或任何类似组合。在替代实施例中，所述层中的任一者都不包括Se。
随后在约400℃到约600℃的温度下使群组I、III、VI前体材料发生反应，以形成I-III-VI2化合物材料。p型半导体130的存在通过提供其上面可形成p型吸收体层155的类似化学和物理表面来实现最佳I-III-VI2化合物形成动力学。在约400℃到约600℃的温度下，p型半导体层130和p型半导体层150将通过类型III元素的交换而互相扩散。另外，碱性材料140中包含的Na将扩散出并进入半导体层150中，从而改进所完成的装置的p型吸收体层155的生长。在沉积后，即刻在约400℃-600℃的温度下对所述层进行热处理。
在对p型吸收体层150进行热处理之后，通过沉积n型结层160来继续光电生产过程。此层160将最终与半导体层150进行交互作用，以形成必需的p-n结165。优选地，在本发明中通过持续一段时间且在较低温度下提供In、Se、Ga以使得所述材料不发生反应以形成CIGS物质而是沉积n型材料来形成结缓冲层。通常，这发生在温度开始低于约450℃时，并持续到约300℃。n型结层的成分中的一者或一者以上可整体或部分扩散到p型吸收体层中从而辅助形成p-n结。对于此层，厚度在约50nm到约500nm的范围内。结层的带隙可大于或可不大于p型吸收体层的带隙。可在小于先前达到(例如在上游p型吸收体层形成步骤期间)的最大温度的环境温度下(具体地说，在300℃到450℃的范围内)形成所述结层。
在一个实施例中，较低温度结过程可在其中热形成p型吸收体层的同一腔室中传递。根据此实施例，将已完成的p型吸收体层暴露于In、Ga、Se蒸汽持续额外时间段。同时，温度从第一温度降低到约300℃到450℃的优选范围。更优选地，较低温度范围为约350℃到400℃。根据此实施例，建立新缓冲层(InGa)ySe。在此实施例中，腔室可因此经配置以在较高温度区域中退火p型吸收前体材料，且随后在同一腔室中的较低温度下游区域中形成结层。
下一层是本征透明氧化层170。所述透明本征氧化层170接下来经沉积以充当具有吸收体的异质结。优选地，透明氧化层170包括II-VI或IIIx VIy化合物，所述化合物充当I-III-VI2吸收体的异质结补伴(hetero-junction partner)。举例来说，氧化物通常为In、Sn或Zn的氧化物。优选地，本征层170包含约10nm到约50nm的厚度。
最后，沉积导电透明氧化层180，以充当电池电极的顶部。氧化物经掺杂以使得其既导电又透明，其用以将电流承载到栅格结构。举例来说，透明导电氧化层180可包含通过CVD或溅镀而沉积的ZnO或ITO。顶部导电层优选地为透明的、导电的，且含有包括类型II元素(例如Cd或Zn)和/或类型III元素(例如In或Al)和/或类型IV元素(例如Sn)和/或类型VI元素(例如氧)的化合物。
栅格结构沉积在导电透明氧化层上方，且由金属层组成，所述金属层的图案经设计以优化收集且最小化暗淡度。优选地，所述栅格包括类型A的薄金属层以确保栅格结构与透明导电氧化物之间的良好欧姆接触，和包括第二金属类型B以将电流承载到外部电路。典型的栅格金属包含类型A：镍(10nm到约50nm)和类型B：铝或银(3μm到5μm)。
尽管已参考特定实施例描述了本发明，但所属领域的技术人员将了解可在不偏离本发明范围的情况下作出各种变化且可用等效物来取代其元件。另外，可在不偏离本发明范围的情况下作出多种修改以使得特定情形或材料适合于本发明教示。
因此，希望本发明不限于揭示为预期用于执行本发明的最佳模式的特定实施例，而是希望本发明将包括属于所附权利要求书的范围和精神内的所有实施例。

Claims (11)

1.一种用于制备光电装置的方法，其包含以下步骤：
a.在衬底上提供p型CIGS半导体层；
b.在约300℃到约450℃之间的温度范围内将所述p型半导体层暴露于In+Se+Ga蒸汽持续2到4分钟，以产生n型半导体层来形成p-n结。
2.一种用于制备光电装置的方法，其包含以下步骤：
a.在衬底上提供p型CIGS半导体层；
b.将所述p型半导体层暴露于In+Se+Ga蒸汽而得到约50nm到约500nm的厚度，以产生n型半导体层来形成p-n结。
3.一种光电装置，其包含：
a.具有CIGS层的衬底；和
b.n型结，其通过在约300℃到约450℃之间的温度范围内提供In+Se+Ga持续2到4分钟而制得。
4.一种光电装置，其包含：
a.具有CIGS层的衬底；
b.和n型结，其通过提供In+Se+Ga而得到约50nm到约500nm厚度，以产生n型层来形成p-n结而制得。
5.一种光电装置，其中p型吸收体层是热形成的且接着被暴露于In+Se+Ga蒸汽持续额外的时间段，且同时将温度从第一温度下降到约300℃到450℃的范围。
6.根据权利要求3所述的装置，其中所述温度范围为约350℃到400℃。
7.根据权利要求5所述的装置，其中所述温度范围为约350℃到400℃。
8.根据权利要求3所述的装置，其中所述装置在所述温度范围内被暴露于In+Se+Ga蒸汽持续充分的时间，以沉积(InxGa1-x)2Se3层。
9.根据权利要求5所述的装置，其中所述装置在所述温度范围内被暴露于In+Se+Ga蒸汽持续充分的时间，以沉积(InxGa1-x)2Se3层。
10.根据权利要求3所述的装置，其中所述(InxGa1-x)2Se3层的沉积是在350℃到370℃下沉积的。
11.根据权利要求5所述的装置，其中所述(InxGa1-x)2Se3层的沉积是在350℃到370℃下沉积的。
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