CN107221574B - 应用于多结太阳能电池的复合dbr结构及其制备方法 - Google Patents
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Abstract
本发明公开了一种应用于多结太阳能电池的复合DBR结构及其制备方法，包括按层状结构依次叠加的3～15层AlAs/AlxOy/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，AlAs/AlxOy/AlGaInAs组合层和AlInP/AlGaInP组合层的层数总和不超过35层，AlInP/AlGaInP组合层是由层状叠加的AlInP层和AlGaInP层构成，AlAs/AlxOy/AlGaInAs组合层是由层状叠加的AlAs/AlxOy组合层和AlGaInAs层构成，其中，AlAs/AlxOy组合层中的AlxOy是由一部分AlAs经过高温湿法氧化而成，且生成的AlxOy折射率比余下的AlAs低，从而能拓宽DBR的反射光子范围。本发明可以避免传统DBR结构反射光子能量的范围不够宽，造成E+ΔE范围内一部分高能粒子不能被有效吸收的情况，将DBR本身的优势作用发挥到极致。
Description
技术领域
本发明涉及太阳能光伏发电的技术领域，尤其是指一种应用于多结太阳能电池的复合DBR结构及其制备方法。
背景技术
近年来，不断有通讯报道航空航天科技取得令人瞩目的新成果，说明其相关领域的技术水也在不断进步和提高。其中，空间电源是航天器通信、数据传输、空间观测以及试验研究的能量来源，随着世界宇航业的迅猛发展和空间竞争的不断加剧，对空间主电源提出了更高的要求：长寿命、高功率、耐高温、低成本，这也是空间电源研究和提升的方向。
高效三结GaAs太阳电池与目前广泛使用的硅太阳电池相比，具有更高的光电转换效率、更强的抗辐照能力、更好的耐高温性能、更小的重量，是国际公认最具竞争力的新一代太阳电池，正在航天领域逐步得到广泛应用。但实际上，GaInP/GaAs/Ge三结太阳能电池作为砷化镓多结电池的主流结构，其带隙组合1.85/1.42/0.67eV对于太阳光光谱并不是最佳的，原因在于Ge底电池的短路电流要比中电池和顶电池的大很多，由于串联结构的电流限制原因，造成很大部分底电池电流转换成热量损失掉。为了提高电池性能，途径一是调整优化带隙组成，即通过提高中顶电池的In组分将带隙调整为1.82～1.87/1.3～1.4/0.67eV；途径二是增加电池结数充分吸收利用光谱能量，比如AlGaInP/AlGaInAs/GaInAs/Ga1-3yIn3yNyAs1-y/Ga1-3xIn3xNxAs1-x/Ge六结太阳能电池结构设计。目前，途径一是日渐趋于成熟的技术路线。设计与实验表明，为了将分段光谱能量充分吸收，各子电池厚度必须足够厚，基本在2～3.5微米，这种情况下，太阳能电池在太空环境中受到大量高能粒子辐照，材料质量变差，尤其是砷化物子电池更为严重，导致各子电池性能有不同程度地衰减，最终影响电池整体的性能。
研究表明，在子电池下方加入适当的DBR(Distributed Brag Reflector分布式布拉格反射层)结构可以在很大程度上使问题得到缓解。这是因为通过调节DBR结构反射相应波段的太阳光，可使初次没有被材料吸收的光子反射回去被二次吸收，相当于变相地增加了“有效吸收厚度”，因此该子电池设计厚度得以大幅降低，电池厚度减薄可以使电池的抗辐照性能显著提升，对于材料质量差少子寿命短的材料还可有效提高少子收集数量。
然而，传统DBR结构的反射波段较窄，不能够很好地涵盖子电池的吸收波段，比如带隙组合1.85/1.33/0.67eV三结电池的中子电池，本该吸收波段670～920nm，但由于材料本身性质的限制，传统DBR(一般为AlGaInAs/AlGaInAs组合层)反射波段仅涵盖150nm左右，导致部分光子不能被反射回有源区再次吸收利用。如果用两种DBR范围的组合层材料简单叠加，每套DBR必须生长足够的对数才会达到理想反射效果，这无疑会增加整体DBR厚度，提高外延源耗及时间成本。
发明内容
本发明的目的在于克服现有技术的缺点与不足，提供了一种应用于多结太阳能电池的复合DBR结构及其制备方法，可以避免传统DBR结构反射光子能量的范围不够宽，造成E+ΔE范围内一部分高能粒子不能被有效吸收的情况，将DBR本身的优势作用发挥到极致，最终提高电池整体光电转换效率。
为实现上述目的，本发明所提供的技术方案如下：
一种应用于多结太阳能电池的复合DBR结构，包括按层状结构依次叠加的3～15层AlAs/AlxOy/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，所述AlAs/AlxOy/AlGaInAs组合层和AlInP/AlGaInP组合层的层数总和不超过35层，且该AlAs/AlxOy/AlGaInAs组合层中的x＝1,2,3,4…，y＝1,2,3,4…；所述AlInP/AlGaInP组合层是由层状叠加的AlInP层和AlGaInP层构成，所述AlAs/AlxOy/AlGaInAs组合层是由层状叠加的AlAs/AlxOy组合层和AlGaInAs层构成，其中，所述AlAs/AlxOy组合层中的AlxOy是由一部分AlAs经过高温湿法氧化而成，且生成的AlxOy折射率比余下的AlAs低，从而能拓宽DBR的反射光子范围。
所述AlInP层、AlGaInP层、AlAs/AlxOy组合层、AlGaInAs层的厚度设计遵循公式：
式中，d为厚度，λ为预计反射波段的中心反射波长，n为对应材料的折射率，其中，AlAs/AlxOy组合层选用AlxOy的折射率。
上述应用于多结太阳能电池的复合DBR结构的制备方法，包括以下步骤：
1)采用金属有机物化学气相沉积技术，在外延生长过程中进行沉积：按层状结构依次叠加3～15层AlAs/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，得到所需的样品，其中，所述AlAs/AlGaInAs组合层是由层状叠加的AlAs层和AlGaInAs层构成；
2)将样品放置在反应舟内；
3)将反应舟置放在密闭腔室，腔室压力恒定，设置温度处于50～300℃范围内；
4)以氮气为载气，将载有水蒸气的混合气通入腔室，并记录氧化时间，其中在氧化的过程当中，AlAs层的部分结构被氧化，生成AlxOy和AsH3有毒气体，即所述AlAs层最终会被氧化成所需的AlAs/AlxOy组合层，且AlAs的氧化总深度不超过电池芯片长度的2/3；
5)将AsH3有毒气体排出，并进行妥善处理。
本发明与现有技术相比，具有如下优点与有益效果：
1、本发明的复合DBR结构联合高温湿法氧化的工艺较传统结构工艺有很大优势，一方面，采用AlAs/AlGaInAs、AlInP/AlGaInP组合DBR加氧化的方法可以在保持反射率效果的基础上展宽反射范围，使透射的光子被二次吸收的几率增加，有利于提高电池效率；另一方面，高温湿法工艺所需装置简单，控制参数为氧化炉压力、氧化温度和时间，在芯片端容易实现稳定工艺。此外，本发明的复合DBR总层数较常规DBR几乎没有增加，即不会增加外延成本。总之，本发明的复合DBR结构及氧化工艺可以使DBR的反射范围展宽到基本覆盖其子电池的吸收带宽，可进一步减薄基区厚度，降低外延成本，使砷化物子电池抗辐照性能得到一定程度的提升，并使一些材料质量差少子扩散长度较小(如：GaInNAs材料)的问题得到进一步缓解。
2、本发明的关键在于通过控制高温湿法氧化的时间等参数，可以准确控制高铝层的氧化深度，保证电池器件整体导通(保留的部分铝砷起连通电池作用，消除AlxOy不导电的影响)，在提高太阳能电池转换效率的研究中，本发明的复合DBR结构作用可以得到更为极致地应用。
附图说明
图1为本发明所述复合DBR结构示意图。
图2为本发明所述复合DBR经高温湿法氧化后的效果示意图之一
图3为本发明所述复合DBR经高温湿法氧化后的效果示意图之二。
图4为含复合DBR结构的四结太阳能电池示意图。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
如图1所示，本实施例所提供的复合DBR结构，包括按层状结构依次叠加的3～15层AlAs/AlxOy/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，所述AlAs/AlxOy/AlGaInAs组合层和AlInP/AlGaInP组合层的层数总和不超过35层，且该AlAs/AlxOy/AlGaInAs组合层中的x＝1,2,3,4…，y＝1,2,3,4…；所述AlInP/AlGaInP组合层是由层状叠加的AlInP层和AlGaInP层构成，所述AlAs/AlxOy/AlGaInAs组合层是由层状叠加的AlAs/AlxOy组合层和AlGaInAs层构成，其中，所述AlAs/AlxOy组合层中的AlxOy(即Al的氧化物)是由一部分AlAs经过高温湿法氧化而成，即AlAs/AlxOy组合层实质是由AlAs层通过高温湿法氧化工艺转变而成，具体请见图2和图3所示，且生成的AlxOy折射率比余下的AlAs低，由于生成物AlxOy具有更低的折射率，这样可使得复合DBR反射光子范围拓宽，而保留的部分AlAs起连通电池作用，消除AlxOy不导电的影响。
此外，所述AlInP层、AlGaInP层、AlAs/AlxOy组合层、AlGaInAs层的厚度设计遵循公式：
式中，d为厚度，λ为预计反射波段的中心反射波长，n为对应材料的折射率，其中，AlAs/AlxOy组合层选用AlxOy的折射率。
如图4所示，为含本实施例上述复合DBR结构的四结太阳能电池，该四结太阳能电池是采用金属有机物化学气相沉积(MOCVD)技术，外延生长过程中沉积复合DBR，电池芯片制程中添加高温湿法氧化的工艺流程。其中，所述四结太阳能电池以Ge单晶片为衬底，在所述Ge衬底上按照层状叠加结构由下至上依次设置有GaInP/GaInAs渐变缓冲层、第一套复合DBR、GaInAs子电池、第二套复合DBR、AlGaInAs子电池和AlGaInP子电池，各子电池之间由隧道结连接。
所述第一套复合DBR的反射波长为780～950nm，AlAs/AlxOy/AlGaInAs组合层的层数为8层，AlInP/AlGaInP组合层的层数为18层。
所述GaInAs子电池中GaInAs材料的光学带隙约为1.25～1.3eV。
所述第二套复合DBR的反射波长为600～780nm，AlAs/AlxOy/AlGaInAs组合层的层数为6层，AlInP/AlGaInP组合层的层数为14层。
所述AlGaInAs子电池中AlGaInAs材料的光学带隙约为1.5～1.6eV。
所述AlGaInP子电池中AlGaInP材料的光学带隙约为2.1～2.15eV。
本实施例上述的高温湿法氧化工艺作为一种特殊工艺处理步骤，设在芯片制程中的适当工艺段(本实施例优选安排在切割且蒸镀电极保护层之后)，经高温湿法氧化后，复合DBR中的一部分AlAs被氧化生成AlxOy和AsH3有毒气体，具体工艺步骤如下：
步骤一：将裸露出切割边的样品(该样品上已沉积有按层状结构依次叠加的3～15层AlAs/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，其中所述的AlAs/AlGaInAs组合层是由层状叠加的AlAs层和AlGaInAs层构成)放置在反应舟内；
步骤二：反应舟置放在密闭腔室，腔室压力恒定(本实施例优先选用1atm)，温度100～300℃(本实施例优先选用260℃)；
步骤三：以氮气为载气，将载有水蒸气的混合气通入腔室，并记录氧化时间，其中在氧化的过程当中，AlAs层的部分结构被氧化，生成AlxOy和AsH3有毒气体，即所述AlAs层最终会被氧化成所需的AlAs/AlxOy组合层；
步骤四：将尾气(具体是AsH3有毒气体)排出，进行专业妥善处理(本实施例优选通入喷淋式尾气处理器)。
此外，经多次实验验证AlAs氧化总深度不超过电池芯片长度的2/3，而较佳氧化层效果示意图请参见图2和图3所示。
经验证，利用本方案制备的四结太阳能电池，在各子电池的带隙得以优化基础上，结合使用具有更为优异反光效果的DBR可使GaInAs和AlGaInAs子电池更多地吸收太阳光子，显著减弱其对四结太阳能电池短路电流的限流程度，提高转换效率。分析可知，在AM0条件下，传统DBR结构的四结太阳能电池的短路电流(Isc)为16.0mA/cm2，而具有本发明的复合DBR结构的四结太阳能电池的Isc可达17.0mA/cm2，且其转换效率可提高至33.4％，具体请参见下表1所示。
表1 AM0条件下，含传统DBR结构的四结太阳能电池与含本发明的复合DBR结构的四结太阳能电池的性能比较
| 电池类型 | Isc(mA/cm2) | Voc(mV) | Pm(W/m2) | FF(％) | Eff(％) |
| 传统DBR | 16.0 | 3250 | 441.82 | 85 | 32.6 |
| 复合DBR | 17.0 | 3210 | 452.31 | 83 | 33.4 |
以上所述实施例只为本发明之较佳实施例，并非以此限制本发明的实施范围，故凡依本发明之形状、原理所作的变化，均应涵盖在本发明的保护范围内。
Claims (3)
1.一种应用于多结太阳能电池的复合DBR结构，其特征在于：包括按层状结构依次叠加的3～15层AlAs/AlxOy/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，所述AlAs/AlxOy/AlGaInAs组合层和AlInP/AlGaInP组合层的层数总和不超过35层，且该AlAs/AlxOy/AlGaInAs组合层中的x=1,2,3,4…，y=1,2,3,4…；所述AlInP/AlGaInP组合层是由层状叠加的AlInP层和AlGaInP层构成，所述AlAs/AlxOy/AlGaInAs组合层是由层状叠加的AlAs/AlxOy组合层和AlGaInAs层构成，其中，所述AlAs/AlxOy组合层中的AlxOy是由一部分AlAs经过高温湿法氧化而成，温度是50～300℃，AlAs的氧化总深度不超过电池芯片长度的2/3，所述深度为电池芯片长度方向，且生成的AlxOy折射率比余下的AlAs低，从而能拓宽DBR的反射光子范围。
2.根据权利要求1所述的一种应用于多结太阳能电池的复合DBR结构，其特征在于：所述AlInP层、AlGaInP层、AlAs/AlxOy组合层、AlGaInAs层的厚度设计遵循公式：d=λ/(4n)，式中，d为厚度，λ为预计反射波段的中心反射波长，n为对应材料的折射率，其中，AlAs/AlxOy组合层选用AlxOy的折射率。
3.一种权利要求1所述应用于多结太阳能电池的复合DBR结构的制备方法，其特征在于，包括以下步骤：
1）采用金属有机物化学气相沉积技术，在外延生长过程中进行沉积：按层状结构依次叠加3～15层AlAs/AlGaInAs组合层和5～25层AlInP/AlGaInP组合层，得到所需的样品，其中，所述AlAs/AlGaInAs组合层是由层状叠加的AlAs层和AlGaInAs层构成；
2）将样品放置在反应舟内；
3）将反应舟置放在密闭腔室，腔室压力恒定，设置温度处于50～300℃范围内；
4）以氮气为载气，将载有水蒸气的混合气通入腔室，并记录氧化时间，其中在氧化的过程当中，AlAs层的部分结构被氧化，生成AlxOy和AsH3有毒气体，即所述AlAs层最终会被氧化成所需的AlAs/ AlxOy组合层，且AlAs的氧化总深度不超过电池芯片长度的2/3；
5）将AsH3有毒气体排出，并进行妥善处理。
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