CN104282804A - 一种通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法 - Google Patents
一种通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005987 sulfurization reaction Methods 0.000 title abstract description 12
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 title abstract 7
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 38
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 230000003287 optical effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 238000005243 fluidization Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 40
- 239000010409 thin film Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明涉及一种通过二次硫化热处理改变化学配比的铜锌锡硫（Cu2ZnSnS4）薄膜的制备方法。其特征是采用铜锌锡硫单一靶材磁控溅射铜锌锡硫预制膜，对预制膜进行二次硫化热处理，得到贫铜富锌得优质铜锌锡硫薄膜。对应的带隙由1.42eV变为1.52eV。本方法工艺简单，成本低廉，操作方便，可重复性强，有助于铜锌锡硫吸收层的叠层太阳电池的产业化发展。
Description
技术领域
本发明涉及通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法，采用铜锌锡硫单一靶材磁控溅射铜锌锡硫预制膜，然后对预制膜进行二次硫化热处理来调节铜锌锡硫薄膜中Cu，Zn，Sn，S的相对含量，获得贫铜富锌的铜锌锡硫薄膜，属于薄膜太阳电池材料领域。
背景技术
铜锌锡硫是一种直接带隙化合物半导体，光学带隙约为1.5 eV，其吸收边高能侧吸收系数高达104 cm-1，被用于制备薄膜太阳电池的吸收层。铜锌锡硫作为吸收层，其元素配比是调控薄膜太阳电池光电转换效率的重要因素，而且，一般高转换效率的铜锌锡硫吸收层具有铜少锌多的特点。目前，铜锌锡硫的制备方法有很多，其中采用单一靶材溅射后硫化的方法具有工艺简单，稳定性，均匀性比较好的特点，有利于该类太阳能电池的产业化发展。但是，采用溅射后一次硫化的制备方法无法解决铜锌锡硫薄膜中锡的含量较多的问题，不符合铜少锌多的高效率吸收层的元素配比。而采用通过二次硫化对溅射后薄膜进行热处理，能有效地解决以上问题，达到贫铜富锌的目的。
发明内容
本发明的目的在于克服目前采用一次硫化的方法不能完全解决锡含量较多的问题。本发明采用二次硫化能进一步降低锡的含量，调节铜锌锡硫薄膜的元素配比从而达到贫铜富锌的目的。
本发明的目的是这样实施的：将单一铜锌锡硫靶材进行磁控溅射，衬底采用钠钙玻璃，衬底温度为500oC，溅射功率为60W，通入氩气前真空度为7×10-4Pa, 相同条件制备4个相同的铜锌锡硫预制膜(a),(b),(c),(d)。再对溅射好的预制铜锌锡硫薄膜(b),(c),(d)加入硫粉后进行真空封管。将封管后的铜锌锡硫薄膜(b),(c)进行一次高温快速硫化热处理，其中：薄膜(c)的保温时间为薄膜(b)的一倍。对铜锌锡硫薄膜(d)先进行低温缓慢硫化热处理后，再进行第二次高温快速硫化热处理。X射线能谱分析表明：磁控溅射后的铜锌锡硫薄膜(a)为贫铜富锡薄膜，进行一次高温快速硫化热处理的薄膜(b),(c):锡的含量有所下降，但仍然没有完全解决锡过量的问题，且延长保温时间没有能有效的进一步减少锡的含量。而进行二次硫化热处理的薄膜(d): 锡的含量大幅度的减少并最终形成 Cu/(Zn+Sn)=0.8, Zn/Sn=1.2的贫铜富锌优质薄膜，说明通过二次硫化热处理相对于一次硫化热处理能更有效地减少磁控溅射薄膜锡过量的问题。
本发明调控铜锌锡硫光学带隙的方法的优点是：
（1）工艺简单，可重复性高。
（2）对薄膜元素配比可调，便于进一步进行研究元素配比对器件转换效率的影响。
附图说明
（1）图1是工艺流程图。
（2）图2是制备的铜锌锡硫薄膜硫化前后的X光衍射图。
（3）图3是制备的铜锌锡硫薄膜硫化前后X射线能谱分析及化学配比。
（4）图4是制备的铜锌锡硫薄膜硫化前后的光学吸收谱图。
具体实施方式
实施例
将硫化亚铜，硫化锌，二硫化锡按照摩尔比1:1:1进行混合，采用玛瑙研钵进行研磨，时间为4h，将混合好的粉末进行高温热压，温度为700oC, 得到化学元素配比为2:1:1:4的铜锌锡硫单一靶材，采用射频磁控溅射在钠钙玻璃上溅射铜锌锡硫薄膜，工艺条件为：衬底温度：500oC, 氩气流速：30ccm, 溅射功率：60W，溅射压强：0.1Pa，溅射前真空度：7×10-4Pa.以相同溅射条件得到4个铜锌锡硫预制膜分别用(a),(b),(c),(d)表示。将薄膜(b),(c),(d)分别放入装有10mg硫粉的石英管中，进行真空封管。采用快速退火炉，先将装有薄膜(b)的石英管放于炉内，快速升温至550oC时，保温10min (升温速率为5oC/s)，自然冷却。再将装有薄膜(c)的石英管以同样方法进行热处理，保温时间变为20min。最后将装有薄膜(d)的石英管放于炉内，当退火炉快速温度升至250oC后(升温速率为5oC/s)，再将温度缓慢地升至380oC (升温速率为5oC/min)，之后再快速将温度升至550oC(升温速率为5oC/s)，保温10min，自然冷却。图2为磁控溅射薄膜与不同硫化热处理条件下铜锌锡硫薄膜的X光衍射图，其衍射峰均为铜锌锡硫相，未发现与杂质相关的第二相，说明获得的铜锌锡硫为单一相kesterite结构。比较预制膜(a),一次硫化薄膜(b)和二次硫化薄膜(d) (112) 衍射峰，其衍射峰依次向大角偏移，且半高宽依次变小，说明锡含量在逐渐减少，结晶程度不断提高。图3为磁控溅射与不同硫化热处理条件下铜锌锡硫薄膜的元素配比，磁控溅射后的薄膜(a)为贫铜富锡：Cu/(Zn+Sn)=0.7, Zn/Sn=0.8,薄膜(b)的化学配比为 Cu/(Zn+Sn)=0.93， Zn/Sn=1.1的薄膜。薄膜(c)的化学配比于薄膜(b)基本一致。说明延长保温时间不能有效的减少锡的含量。薄膜(d)的化学配比：Cu/(Zn+Sn)=0.8, Zn/Sn=1.2 为贫铜富锌优质的铜锌锡硫薄膜。图4为磁控溅射薄膜与不同硫化热处理条件下铜锌锡硫薄膜的光学吸收谱。硫化前的铜锌锡硫薄膜带隙为1.42eV(a), 一次硫化后薄膜带隙为1.48eV(b), 二次硫化后薄膜带隙为1.52eV(d),带隙依次变大且逐渐趋近于铜锌锡硫的理想的带隙大小，二次硫化后的薄膜斜率比一次硫化后的大，说明二次硫化的结晶程度相对提高与缺陷相对减少，这有利于转换效率的提高。
Claims (3)
1.一种通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法，其特征在于采用铜锌锡硫单一靶材进行磁控溅射，对溅射后的薄膜进行二次硫化热处理，将获得贫铜富锌的铜锌锡硫薄膜。
2.一种通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法，其特征在于Cu/(Zn+ Sn)=0.8, Zn/Sn=1.2，铜锌锡硫薄膜为锌黄锡矿（Kesterite）结构。
3.按照权利要求1所述的通过二次硫化调节铜锌锡硫薄膜元素配比的制备方法，其特征在于通过对单一靶材磁控溅射的铜锌锡硫薄膜进行二次硫化能有效解决薄膜中锡过量的问题，二次流化后的铜锌锡硫的光学带隙在1.54eV左右。
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| CN106653898A (zh) * | 2016-11-04 | 2017-05-10 | 中利腾晖光伏科技有限公司 | 一种czts太阳能电池 |
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| CN102339903A (zh) * | 2011-07-26 | 2012-02-01 | 友达光电股份有限公司 | 形成光电转换层的方法 |
| CN103172378A (zh) * | 2011-12-21 | 2013-06-26 | 北京有色金属研究总院 | 铜锌锡硫陶瓷靶材及其真空热压制备方法 |
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| CN106653898A (zh) * | 2016-11-04 | 2017-05-10 | 中利腾晖光伏科技有限公司 | 一种czts太阳能电池 |
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