CN105552140B - 高比功率GaAs多结柔性薄膜太阳电池及其制备方法 - Google Patents

高比功率GaAs多结柔性薄膜太阳电池及其制备方法 Download PDF

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CN105552140B
CN105552140B CN201610062060.5A CN201610062060A CN105552140B CN 105552140 B CN105552140 B CN 105552140B CN 201610062060 A CN201610062060 A CN 201610062060A CN 105552140 B CN105552140 B CN 105552140B
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吴洪清
米万里
曹来志
张永
张双翔
徐培强
李俊承
韩效亚
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Abstract

高比功率GaAs多结柔性薄膜太阳电池及其制备方法,涉及砷化镓多结柔性太阳电池生产技术领域。本发明在下电极一侧设置电池外延层,在电池外延层上设置上电极和减反射膜;所述电池外延层包括N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层。本发明产品仅上、下电极,加外延层和减反射膜,并无衬底支撑,具有较高的重量比功率和超薄性的特点,产品厚度仅约10~15μm上,且输出功率互不影响、独立工作。另外,具有弯曲的特性,可大大增加太阳电池的应用范围。

Description

高比功率GaAs多结柔性薄膜太阳电池及其制备方法
技术领域
本发明涉及砷化镓多结柔性太阳电池生产技术领域。
背景技术
我国的太阳电池发展迅速,其中GaAs太阳电池为航天事业承担着重要角色。目前GaAs多结太阳电池主要有以Ge和GaAs为衬底正装多结太阳电池,以及倒置结构的多结太阳电池,其中倒置多结太阳电池因为各结电池带隙较好的匹配全光谱,有助于太阳光吸收,使得其光电转换效率始终远远领先于其它太阳电池,备受人们的青睐。倒装太阳电池虽然转换效率较高,但因键合在Si片上,电池片的重量也不轻,导致重量比功率并不理想;加之使用衬底是刚性材料,应用范围局限于平整的基板。对于太阳电池空间来说,其中一种重要指标就是重量比功率,所以具有较高质量比功率的柔性太阳电池成为当前研究的一大热点。
如图1所示,现有的太阳电池生产步骤如下:
1、外延生长:
采用MOCVD设备在GaAs衬底上依次生长N型GaAs的缓冲层、GaInP腐蚀截止层、N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层完成外延片24的生长。
2、衬底转移:
在电池外延片24的底电池背部和导电类型为P型的转移Si衬底22正面,分别通过电子束依次蒸镀Ti、Pt和Au层,再将蒸镀完电池外延片24与转移Si衬底22通过金属键合层23进行金属键合。
3、衬底剥离:
采用氨水、双氧水腐蚀液去除金属键合后的电池外延结构上的GaAs衬底。
4、电极制作:
采用负性光刻胶工艺光刻电极栅线图形,用电子束和热阻真空蒸镀的方式,在顶电池欧姆接触层上制备金属电极,并通过有机剥离将完成上电极26制作;在转移Si衬底22背面蒸镀制备下电极21。
5、减反射膜:
将完成选择性腐蚀的电池片,采用电子束蒸镀的方法蒸镀TiO2/Al203双层减反射膜25。
6、退火、划片、端面处理完成倒装太阳电池芯片制作。
这种GaInP/GaAs/InGaAs倒装三结太阳电池目前效率最高的效率在32%左右,在光谱AM 0下,标准光强为136.7mw/cm2,输出功率约为43.74 mw/cm2率;以面积12cm2的倒装三结电池芯片为例,电池质量2.25g,质量比功率1945w/kg,已接近理论值,离3000w/kg空间需求还有一定距离。
若能将衬底去除或者采用较轻衬底替代,结果可想而知,重量将大幅降低,相应空间飞行器的发射和运载成本将会得到很好的改善。
发明内容
针对现有技术的不足,本发明目的是提出一种能减轻电池体重量、具有柔韧弯曲,从而提高重量比功率和扩大应用范围的GaAs多结柔性薄膜太阳电池。
本发明包括下电极,在下电极一侧设置电池外延层,在电池外延层上设置上电极和减反射膜;所述电池外延层包括N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层。
本发明产品仅上、下电极,加外延层和减反射膜,并无衬底支撑,具有较高的重量比功率和超薄性的特点,产品厚度仅约10~15μm上,且输出功率互不影响、独立工作。另外,具有弯曲的特性,可大大增加太阳电池的应用范围。
进一步地,本发明在上电极和减反射膜上设置临时保护层,在临时保护层上设置临时柔性载体。
临时保护层的作用在于保护电池正面,避免因临时载体粘附的胶层残留在电池表面,影响柔性电池的表观和电学特性。在临时柔性载体只起到托运的作用,以确保在搬运过程中对产品的保护。使用时仅需通过简单的操作即可去除临时保护层和临时柔性载体。
为了便于粘合和分离,同时,不影响产品的柔性和硬度,所述临时柔性载体为UV膜、热剥离膜、PET衬底、PI柔性衬底或PEN衬底中的任意一种。
所述减反射膜为TiO2/SiO2、TiO2/Al2O3、TiO2/Ta2O5、TiO2/Si3N4、TiO2/Ta2O5/Al2O3、TiO2/Ta2O5/SiO2、TiO2/Si3N4/ Al2O3或TiO2/Si3N4/ SiO2多层结构中的任意一种,TiO2的厚度为1λ/4n,Ta2O5的厚度为1λ/4n,Al2O3的厚度为1λ/4n,SiO2的厚度为1λ/4n,Si3N4的厚度为1λ/4n,其中λ为波长,单位nm;n为介质膜的折射系数。砷化镓多结太阳电池不仅利用可见光,不可见的紫外光和红外光仍然将其转换为电能,可以吸收从300nm到2000nm波段,这也就是砷化镓多结太阳电池高效性的特点。利用多层结构形成减反射膜的结构可以降低太阳光各个波段的反射率,从而太阳电池的光电转换效率。
所述下电极为Ag、Al、Au、Ti、Pd、Pt、Ni、In中的任意一种或几种,下电极的厚度大于1μm。通过加压和400℃高温的作用,金属之间会相互扩散融合在一起,金属厚度不能小于1μm,避免因金属之间结合的力不够,造成下电极分层,影响太阳电池的电性能。
本发明另一目的是提出以上高比功率GaAs多结柔性薄膜太阳电池的制备方法。
本发明包括以下步骤:
1)生长外延片:在第一临时衬底上依次生长N型GaAs的缓冲层、GaInP腐蚀截止层、N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层;
2)在P型InGaAs接触层上制作金属键合层;
3)在第二临时衬底的正表面制作金属键合层;
4)衬底转移:将第二临时衬底的金属键合层与外延片的金属键合层压相对,通过金属键合,将外延片与第二临时衬底键合,取得键合好的电池片;
5)衬底剥离:去除键合好的电池片上外延片的第一临时衬底,直至露出GaInP腐蚀截止层;
6)上电极制作:去除所述GaInP腐蚀截止层,在N型GaAs接触层上制作上电极;
先采用负性光刻胶工艺光刻电极栅线图形,用电子束和热阻真空蒸镀的方式,蒸镀腔体温度小于100℃,在外延片上制备金属电极,并通过有机剥离形成上电极;
7)将外延片中N型GaAs接触层有选择性腐蚀去除上电极以外部分;
8)在外延片的上电极以外区域,采用电子束或PECVD沉积的方法在外延片上蒸镀减反射膜;
9)套刻将上电极一侧的减反射膜蚀刻开孔,高温退火形成欧姆接触;
10)涂柔性保护层后,使用化学溶液去除第二临时衬底;
11)划片:切除非电池区域部分留下完整电池芯片;
12)端面腐蚀:采用化学溶液将电池芯片侧面腐蚀清洗切割残渣颗粒,并去胶清洗。
本工艺简单,操作方便,不仅能有效地解决薄膜电池因为柔性衬底与外延层膨胀系数不一,而引起的电池表面鼓泡、失效的问题,而且能够减轻电池体重量,提高了该电池的重量比功率,减轻了火箭的发射和卫星的飞行负担。
本发明所述步骤2)中金属键合层采用Ag、Al、Au、Ti、Pd、Pt、Ni或In等金属材料的任意一种或几种。所述步骤3)中金属键合层采用Ag、Al、Au、Ti、Pd、Pt、Ni或In金属材料的任意一种或几种。通过加压和400℃高温的作用,金属之间相互扩散融合紧密结合在一起,形成非常牢固的金属键,这样避免空间恶劣的环境引起太阳电池的失效或衰减。
在所述步骤9)后,于在上电极和减反射膜上制作临时保护层,然后再在临时保护层上设置临时柔性载体,再去除第二临时衬底。以此在上电极和减反射膜上设置临时保护层,在临时保护层上设置临时柔性载体。在临时柔性载体只起到托运的作用,以确保在搬运过程中对产品的保护。使用时仅需通过简单的操作即可去除临时保护层和临时柔性载体。
所述临时柔性载体采用UV膜、热剥离膜、PET衬底、PI柔性衬底或PEN衬底中的任意一种。
本发明所述步骤3)中,临时衬底正面有机清洗。键合层蒸镀前后注意晶片表面的洁净程度,如有颗粒或蒸镀过程溅金属,键合时会引起衬底剥离后芯片表面的鼓起或者碎裂。
在所述步骤6)中,在电池表面制作电极栅线图形时,必须注意表面的洁净,电极图形具有一定的垂直性,避免栅线电极在退火是无法有效融合,影响电极的牢固性,从而导致电池的可靠性影响!
在所述步骤7)中,选择性腐蚀两面同时蚀刻,注意溶液配制的量,避免刻蚀的不均匀现象。
在所述步骤10)中,在临时载体贴片时,注意需从一边均匀擀膜,避免有气泡影响粘附效果,另外,压合的压力不宜过大,否则电池破片影响其成品率。
在所述步骤13)中,临时载体移除前,保证电池与基板粘附平整,牢固后方可移除临时载体,且温度不宜超过200℃,避免载体剥离后残余物难以去除。
本发明关键在于使用倒装电池结构,键合层金属经过临时衬底剥离后作为电池的下电极;其次,采用具有热敏作用的柔性临时载体,该薄膜衬底具有一定硬度可以支撑剥离下来的电池体,另外具有柔韧性可以弯曲,便于电池非平面的粘结,更重要的是加热到特定的温度将会使之粘性失效,让电池体与载体自然分离,并且表面不会有任何残留物,使仅仅10微米多厚电池体完成器件制作,达到零衬底的电池结构。
附图说明
图1为现有技术产品的结构示意图。
图2 为本发明制作过程中的外延片结构示意图。
图3为本明产品临时柔性载体未去除的结构示意图。
图4为本明产品的结构示意图。
图5为本明产品的平面示意图。
具体实施方式
一、生产工艺:
1、外延片生长:
采用MOCVD设备在厚度为350μm的GaAs衬底10上依次生长N型GaAs的缓冲层11、GaInP腐蚀截止层12、N型GaAs接触层13、GaInP顶电池14、第一隧穿结15、GaAs中电池16、第二隧穿结17、InGaAs底电池18和P型InGaAs接触层19,完成具有临时衬底的外延片的外延层生长,如图2所示。以下统称为电池外延层。
2、电池外延片键合层蒸镀:选取两片所述电池外延片激光打标进行编号,使用丙酮、异丙醇有机超声清洗10min、干燥15min,在P型InGaAs接触层19上分别通过电子束依次蒸镀Ti、Pd、Ag和Au层,蒸镀层的总厚度不低于2μm。
3、临时衬底键合层蒸镀:选取一片厚270μm单面抛光砷化镓临时衬底,经有机超声10min、干燥15min,并在干燥后的砷化镓衬底的正表面通过电子束依次蒸镀Ti、Pt和Au键合层31,膜厚不低于2μm。
4、衬底转移:
将上述蒸镀后的外延片上蒸镀层与砷化镓临时衬底上蒸镀层相对合在一起,经过高温加热到400℃、加压到5000kg/cm2进行键合20min,使电池片与砷化镓衬底牢牢地粘附起来,取得键合好的电池片。
5、衬底剥离:
在键合好的电池片上的砷化镓临时衬底表面涂胶保护后,浸入由体积比为1∶10的氨水和双氧水配制成的混合溶液中,经30min后,去除电池片的外延片上的衬底10,露出GaInP腐蚀截止层12,并经过QDR冲洗、脱水,烘干待用。
6、上电极制作:
将完成衬底剥离后的制品浸入由体积比为1∶2的盐酸和磷酸混合组成的溶液中去除截止层12,露出N型GaAs接触层13,并经过丙酮、酒精有机超声清洗,QDR清洗旋干后,采用负性光刻胶工艺经黄光涂胶、光刻、显影等电极栅线图形,用电子束和热阻真空蒸镀的方式,蒸镀腔体温度小于100℃,在具有砷化镓临时衬底的电池外延层32上制备金属电极,并通过有机剥离将完成正面电池上电极34制作。
7、选择性腐蚀:
以柠檬酸、双氧水和水以1∶2∶2的体积比混合,形成混合溶液。
将制作好上电极34的制品浸于混合溶液中,在40℃下有选择性地蚀刻上电极34以外的N型GaAs接触层13,经过QDR冲洗,旋干待用。
8、减反射膜:
将完成选择性腐蚀的电池片,采用电子束或PECVD沉积的方法在转移的电池外延层32上蒸镀TiO2/Si3N4/SiO2多层减反射膜33,其中,TiO2膜厚50nm,Si3N4膜厚25nm,SiO2膜厚95nm,并通过套刻的方式制作图形将电极焊线部位的减反射膜蚀刻开口便于焊接、测试。
上述减反射膜也可以采用TiO2/SiO2、TiO2/Al2O3、TiO2/Ta2O5、TiO2/Si3N4、TiO2/Ta2O5/Al2O3、TiO2/Ta2O5/SiO2或TiO2/Si3N4/ Al2O3多层结构中的任意一种,TiO2的厚度为1λ/4n,Ta2O5的厚度为1λ/4n,Al2O3的厚度为1λ/4n,SiO2的厚度为1λ/4n,Si3N4的厚度为1λ/4n,其中λ为波长,单位nm;n为介质膜的折射系数。
9、退火:采用400℃高温退火20min,形成良好的欧姆接触。
10、临时柔性载体:
在退火好的电池表面涂一层容易去除的光刻胶作为临时保护层35,使用与电池晶圆同等大小的热剥离膜贴在临时保护层35的外表面,用倒膜机压合10~20秒,形成临时柔性载体层36。
临时保护层35的材料可选自V膜、热剥离膜、PET衬底、PI柔性衬底或PEN衬底中的任意一种。
然后浸入由体积比为1∶10的氨水和双氧水组成的混合溶液约30min,去除砷化镓临时衬底,露出键合层31截止。
11、划片
采用金刚石刀片切割或激光切割对电池芯片分割,将非电池区域部分切除留下完整电池芯片。
12、端面腐蚀
采用体积比为1∶2∶2的柠檬酸、双氧水和水混合溶液,在40℃下浸3~5min,将切割好电池芯片侧面腐蚀清洗掉切割残渣颗粒。
可依据客户实际需求,选择不同尺寸的电池芯片,将其键合层31焊接或者用导电胶粘合在具有一定强度柔性板材上,再用金属互联条将各芯片间的串并联串接形成一个太阳电池组件,该组件具有特定的光电转换功率。
至此,完成了高比功率GaAs多结柔性薄膜太阳电池的制作。
用户使用说明:取高比功率GaAs多结柔性薄膜太阳电池在90~110℃条件下加热,即可方便地分离去除临时柔性载体层36,再在去除了临时柔性载体层36的产品外表面用有机清洗剂将临时保护层35清洗干净,就可正常使用了。
二、产品结构特点:
如图4所示,制成的产品包括键合层(即下电极)31,在下电极31一侧设置电池外延层32,在电池外延层32的表面设置ARC减反射膜33和上电极34。其中,电池外延层包括N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层。
图5中,为设置在同一侧的两个上电极34,两个上电极34之间通过电导材料连接,在ARC减反射膜33正面可见电极栅线。
三、产品特点:
由于375μm厚的电池衬底10完全去除,电池质量减轻很多,所以提高了太阳电池的重量比功率;另外,电池体很薄,具有很好的柔韧性,增加了太阳电池的使用范围。

Claims (7)

1.高比功率GaAs多结柔性薄膜太阳电池,包括下电极,在下电极一侧设置电池外延层,在电池外延层上设置上电极和减反射膜;所述电池外延层包括N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层,所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,包括以下步骤:
1)生长外延片:在第一临时衬底上依次生长N型GaAs的缓冲层、GaInP腐蚀截止层、N型GaAs接触层、GaInP顶电池、第一隧穿结、GaAs中电池、第二隧穿结、InGaAs底电池和P型InGaAs接触层;
2)在P型InGaAs接触层上制作金属键合层;
3)在第二临时衬底的正表面制作金属键合层;
4)衬底转移:将第二临时衬底的金属键合层与外延片的金属键合层压相对,通过金属键合,将外延片与第二临时衬底键合,取得键合好的电池片;
5)衬底剥离:去除键合好的电池片上外延片的第一临时衬底,直至露出GaInP腐蚀截止层;
6)上电极制作:去除所述GaInP腐蚀截止层,在N型GaAs接触层上制作上电极;
先采用负性光刻胶工艺光刻电极栅线图形,用电子束和热阻真空蒸镀的方式,蒸镀腔体温度小于100℃,在外延片上制备金属电极,并通过有机剥离形成上电极;
7)将外延片中N型GaAs接触层有选择性腐蚀去除上电极以外部分;
8)在外延片的上电极以外区域,采用电子束或PECVD沉积的方法在外延片上蒸镀减反射膜;
9)套刻将上电极一侧的减反射膜蚀刻开孔,高温退火形成欧姆接触;
10)涂柔性保护层后,使用化学溶液去除第二临时衬底;
11)划片:切除非电池区域部分留下完整电池芯片;
12)端面腐蚀:采用化学溶液将电池芯片侧面腐蚀清洗切割残渣颗粒,并去胶清洗。
2.根据权利要求1所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:所述步骤2)中金属键合层采用Ag、Al、Au、Ti、Pd、Pt、Ni或In材料至少任意一种。
3.根据权利要求1所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:所述步骤3)中金属键合层采用Ag、Al、Au、Ti、Pd、Pt、Ni或In材料至少任意一种。
4.根据权利要求1所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:在所述步骤9)后,于在上电极和减反射膜上制作临时保护层,然后再在临时保护层上设置临时柔性载体,再去除第二临时衬底。
5.根据权利要求4所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:所述临时柔性载体采用UV膜、热剥离膜、PET衬底、PI柔性衬底或PEN衬底中的任意一种。
6.根据权利要求1所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:所述减反射膜为TiO2/SiO2、TiO2/Al2O3、TiO2/Ta2O5、TiO2/Si3N4、TiO2/Ta2O5/Al2O3、TiO2/Ta2O5/SiO2、TiO2/Si3N4/ Al2O3或TiO2/Si3N4/ SiO2多层结构中的任意一种;TiO2的厚度为1λ/4n,Ta2O5的厚度为1λ/4n,Al2O3的厚度为1λ/4n,SiO2的厚度为1λ/4n,Si3N4的厚度为1λ/4n,其中λ为波长,单位nm;n为介质膜的折射系数。
7.根据权利要求1所述高比功率GaAs多结柔性薄膜太阳电池的制备方法,其特征在于:所述下电极为Ag、Al、Au、Ti、Pd、Pt、Ni、In中的至少任意一种,下电极的厚度大于1μm。
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