CN106449812B - 溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法 - Google Patents
溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法 Download PDFInfo
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- SEAVSGQBBULBCJ-UHFFFAOYSA-N [Sn]=S.[Cu] Chemical compound [Sn]=S.[Cu] SEAVSGQBBULBCJ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000010409 thin film Substances 0.000 title claims abstract description 38
- 238000004544 sputter deposition Methods 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 31
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000010408 film Substances 0.000 claims abstract description 53
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 238000004073 vulcanization Methods 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000005361 soda-lime glass Substances 0.000 claims description 10
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- -1 compound copper sulfide Chemical class 0.000 abstract 1
- 229910052802 copper Inorganic materials 0.000 abstract 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- DZXKSFDSPBRJPS-UHFFFAOYSA-N tin(2+);sulfide Chemical compound [S-2].[Sn+2] DZXKSFDSPBRJPS-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
本发明公开了一种采用射频磁控溅射锡（Sn）靶和硫化铜（CuS）靶制备铜锡硫（Cu2SnS3，CTS）薄膜的方法，其特征在于采用了金属单质锡靶和化合物硫化铜靶混合溅射制备铜锡硫薄膜预制层，然后对预制层进行软退火及高温硫化，得到铜锡硫薄膜；该方法与传统的溅射金属单质铜靶和锡靶相比，能够更好地控制薄膜体内的载流子浓度；与溅射硫化铜靶和硫化锡靶相比，能够解决高温硫化，薄膜易从衬底脱落和产生孔洞的问题；溅射制备的预制层经过软退火及高温硫化后，得到均匀致密、光电特性较优的铜锡硫薄膜，尝试将其用于制备铜锡硫薄膜电池，最终获得了1.32%的光电转换效率；为制作铜锡硫薄膜太阳电池提供了一种较佳的吸收层制备方案。
Description
技术领域
本发明涉及一种溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，属于光电材料新能源技术领域。
背景技术
铜锌锡硫(Cu2ZnSnS4,CZTS)被认为是一种最具发展潜能的新型薄膜太阳电池材料，其光吸收系数大，并且禁带宽度约为1.45eV与太阳光谱形成较佳匹配。在过去的几年间，CZTS薄膜太阳电池被广泛地研究且取得了较大的进展。然而，作为四元化合物半导体，CZTS在制备过程中很容易产生二次相，如Cu2S、SnS2和Cu2SnS3等，对薄膜的光学、电学性能产生不利影响。相比而言，三元铜锡硫(Cu2SnS3,CTS)化合物元素种类少，CTS相平衡区域较宽，组分比例更容易控制，并且CTS也是带隙值约为1.0eV的直接带隙半导体，其光吸收系数大(>104cm-1)，导电类型为P型，适宜用作薄膜太阳电池的吸收层材料。据第一性原理计算，CTS薄膜太阳电池的理论转换效率约为30％，目前纯相的CTS薄膜太阳电池最高效率为4.29％，由Ayaka Kanai研究小组用共蒸发法制得；
溅射法制备Cu2SnS3薄膜，很多报道中都是先采用溅射金属单质靶制备预制层，后硫化得到CTS薄膜，但这种方法制备的薄膜很容易出现元素分布不均匀、载流子浓度高的现象(在1018～1020cm-3数量级)，而对于CTS薄膜太阳电池而言，吸收层过高的载流子浓度会使得少数载流子扩散长度减小，降低了光生载流子的收集从而降低短路电流。采用溅射化合物靶制备铜锡硫薄膜的报道很少，而Chierchia研究小组用溅射硫化铜(CuS)和硫化亚锡(SnS)的方法制备出的CTS薄膜，运用于薄膜太阳电池上获得了3.05％的光电转换效率，这也是目前溅射法制备CTS薄膜太阳电池获得的最高效率。虽然效率较高但是CTS薄膜的晶粒细小造成大量晶界，增加了载流子的复合几率。为了提高薄膜的晶体质量，Chierchia研究小组升高了硫化温度，虽然晶体质量提高、晶粒尺寸变大，但薄膜变得疏松多孔，用其制备的薄膜太阳电池开路电压大幅降低。采用金属单质靶和化合物靶混合溅射制备铜锡硫薄膜的方法还未见有相关报道，而本发明采用射频磁控溅射锡靶和硫化铜靶制备铜锡硫薄膜预制层，然后对预制层进行软退火及高温硫化得到的铜锡硫薄膜，表面致密、结晶质量较好，晶粒尺寸大并且通过控制薄膜组分能够使其载流子浓度在1017cm-3数量级，较适合用做薄膜太阳电池的吸收层。
发明内容
本发明的目的在于针对现有溅射法制备铜锡硫薄膜存在的问题，提供一种更有效的获得较佳质量铜锡硫薄膜的制备方法；
本发明所涉及的铜锡硫薄膜电池的制备方法按以下步骤实施：
(1)铜锡硫薄膜预制层的制备：在钠钙玻璃上或是镀钼的钠钙玻璃上用射频磁控溅射法溅射锡金属层，然后在锡金属层上溅射硫化铜制备出铜锡硫薄膜的预制层；
(2)预制层的软退火：将铜锡硫薄膜的预制层放置在退火炉中，氮气作为保护气，在260℃下对预制层进行低温退火，保持30分钟后让其自然冷却至室温；
(3)高温硫化：将软退火后的预制层取出，放置在封闭的石墨舟中，以硫粉作为硫源，硫化炉的工作压强为5000Pa，硫化温度为570℃保持15分钟，硫化结束后自然冷却到室温，得到铜锡硫薄膜；
(4)铜锡硫薄膜电池的制备：在铜锡硫薄膜(以镀钼钠钙玻璃为衬底)上沉积CdS缓冲层，然后用磁控溅射法制备ZnO/AZO窗口层，最后采用热蒸发法蒸镀上Ni-Al电极制备出结构为SLG/Mo/CTS/CdS/ZnO/AZO/Ni-Al的铜锡硫薄膜电池；
本发明与现有技术相比，具有的有益效果是：
该方法能够更好、更容易地控制薄膜体内的载流子浓度，提高少数载流子的收集率，也能够解决高温硫化过程中薄膜易从衬底脱落和产生孔洞的问题。所制备的铜锡硫薄膜表面致密、结晶质量较好，晶粒尺寸大并且载流子浓度在1017cm-3数量级，较适合用做薄膜太阳电池的吸收层。
附图说明
图1为本发明制备的铜锡硫薄膜的XRD图；
图2为本发明制备的铜锡硫薄膜的Raman图；
图3中，(a)为本发明制备的铜锡硫薄膜的表面形貌图；(b)为本发明制备的铜锡硫薄膜的截面图；
图4为本发明制备的铜锡硫薄膜(αhν)2与hν的关系图；
图5为本发明制备的铜锡硫薄膜的元素比例及部分电学性质；
图6为本发明制备的铜锡硫薄膜电池的J-V特性曲线图。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围；此外应理解，在阅读了本发明讲述的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围；
实施例1
操作步骤如下：
1.在磁控溅射薄膜的真空腔室内放入钠钙玻璃或是镀钼的钠钙玻璃衬底，将腔室抽至背底真空5×10-4Pa；
2.将衬底台的转速调至7转/分钟，用50W的射频溅射功率在衬底上溅射锡金属层，再用100W的射频溅射功率溅射硫化铜，以Sn/CuS的顺序溅射三个周期制备厚度大概为800nm的铜锡硫薄膜预制层，并且衬底不加温；
3.将铜锡硫薄膜的预制层放置在退火炉中，将退火炉抽至低真空后冲入氮气作为保护气，直到退火炉中气压达到3000Pa对预制层进行软退火。以35℃/min的升温速率，从室温加热到260℃，保持30分钟后让其自然冷却至室温；
4.高温硫化：取出软退火后的预制层，放置在封闭的石墨舟中，石墨舟中装有0.5g的硫粉作为硫源，将硫化炉抽至低真空后冲入氮气使得硫化炉的工作压强为5000Pa，然后以30℃/min的升温速率，从室温加热到570℃，保持15分钟，最后让其自然冷却至室温，得到铜锡硫薄膜；
5.用化学水浴法在铜锡硫薄膜上制备50nm厚的CdS缓冲层，然后用磁控溅射法制备200nm左右的ZnO/AZO窗口层，最后采用热蒸发法蒸镀上Ni-Al电极制备出结构为SLG/Mo/CTS/CdS/ZnO/AZO/Ni-Al的铜锡硫薄膜电池；
实施例2
操作步骤如下：
1.在磁控溅射薄膜的真空腔室内放入钠钙玻璃或是镀钼的钠钙玻璃衬底，将腔室抽至背底真空5×10-4Pa；
2.将衬底台的转速调至7转/分钟，用50W的射频溅射功率在衬底上溅射锡金属层，再用100W的射频溅射功率溅射硫化铜，以Sn/CuS的顺序溅射三个周期制备厚度大概为800nm的铜锡硫薄膜预制层，并且衬底不加温；
3.将铜锡硫薄膜的预制层放置在退火炉中，将退火炉抽至低真空后冲入氮气作为保护气，直到退火炉中气压达到3000Pa对预制层进行软退火。以30℃/min的升温速率，从室温加热到300℃，保持30分钟后让其自然冷却至室温；
4.高温硫化：取出软退火后的预制层，放置在封闭的石墨舟中，石墨舟中装有0.5g的硫粉作为硫源，将硫化炉抽至低真空后冲入氮气使得硫化炉的工作压强为5000Pa，然后以25℃/min的升温速率，从室温加热到560℃，保持15分钟，最后让其自然冷却至室温，得到铜锡硫薄膜；
用磁控溅射法在铜锡硫薄膜上制备50nm厚的CdS缓冲层，然后用磁控溅射法制备200nm左右的ZnO/AZO窗口层，最后采用热蒸发法蒸镀上Ni-Al电极制备出结构为SLG/Mo/CTS/CdS/ZnO/AZO/Ni-Al的铜锡硫薄膜电池。
Claims (5)
1.一种采用溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，其特征在于，包括如下步骤：
(1)铜锡硫薄膜预制层的制备：在钠钙玻璃上或是镀钼的钠钙玻璃上用射频磁控溅射法溅射锡金属层，然后在锡金属层上溅射硫化铜制备出铜锡硫薄膜的预制层；
(2)预制层的软退火：将铜锡硫薄膜的预制层放置在退火炉中，氮气作为保护气，在260℃下对预制层进行低温退火，保持30分钟后让其自然冷却至室温；
(3)高温硫化：将软退火后的预制层取出，放置在封闭的石墨舟中，以硫粉作为硫源，硫化炉的工作压强为5000Pa，硫化温度为570℃保持15分钟，硫化结束后自然冷却到室温，得到铜锡硫薄膜；
(4)采用化学水浴法在铜锡硫薄膜上沉积一层50nm厚的CdS缓冲层，然后用溅射法制备200nm的ZnO/AZO窗口层，最后采用热蒸发法蒸镀上Ni-Al电极制备出铜锡硫薄膜电池；
其中，所述步骤(1)中，磁控溅射薄膜的真空腔室背底真空为5×10-4Pa，工作压强为0.3Pa；磁控溅射薄膜的腔室中靶表面与衬底的间距为10cm，衬底台的转速为7转/分钟，并且不对衬底进行加温；在钠钙玻璃上或是镀钼的钠钙玻璃上用射频磁控溅射锡和硫化铜靶制备铜锡硫薄膜的预制层，其溅射功率分别为Sn：50W，CuS：100W。
2.如权利要求1所述的一种采用溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，其特征在于，所述步骤(1)中，在钠钙玻璃上或镀钼的钠钙玻璃上用射频磁控溅射锡和硫化铜靶制备铜锡硫薄膜的预制层，其溅射顺序为Sn/CuS/Sn/CuS/Sn/CuS三个周期；所制备的铜锡硫薄膜的预制层，其总厚度为800nm。
3.如权利要求1所述的一种采用溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，其特征在于，所述步骤(2)中，将铜锡硫薄膜的预制层放置在退火炉中，将退火炉抽至低真空后冲入氮气作为保护气，直到退火炉中气压达到3000Pa；对放入退火炉中的预制层进行软退火，以35℃/min的升温速率，从室温加热到260℃，保持30分钟后让其自然冷却至室温。
4.如权利要求1所述的一种采用溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，其特征在于，所述步骤(3)中，将软退火后的预制层取出，放置在封闭的石墨舟中，石墨舟中装有0.5g的硫粉作为硫源；先将硫化炉抽至低真空，然后冲入氮气使得硫化炉的工作压强为5000Pa；以30℃/min的升温速率，从室温加热到570℃，保持15分钟后让其自然冷却至室温，得到铜锡硫薄膜。
5.如权利要求1所述的一种采用溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法，其特征在于，所述步骤(4)中，用化学水浴法在铜锡硫薄膜上制备50nm厚的CdS缓冲层，然后用磁控溅射法制备200nm的ZnO/AZO窗口层，最后采用热蒸发法蒸镀上Ni-Al电极制备出结构为SLG/Mo/CTS/CdS/ZnO/AZO/Ni-Al的铜锡硫薄膜电池。
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