CN104282804B - 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
- Publication number
- CN104282804B CN104282804B CN201410326643.5A CN201410326643A CN104282804B CN 104282804 B CN104282804 B CN 104282804B CN 201410326643 A CN201410326643 A CN 201410326643A CN 104282804 B CN104282804 B CN 104282804B
- Authority
- CN
- China
- Prior art keywords
- zinc
- tin
- copper
- sulfur
- cure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000013077 target material Substances 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052718 tin Inorganic materials 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 10
- 238000004544 sputter deposition Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 39
- 239000010409 thin film Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 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
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
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。
技术背景
铜锌锡硫是一种直接带隙化合物半导体,光学带隙约为1.5eV,其吸收边高能侧吸收系数高达104cm-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500℃,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700℃,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:500℃,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550℃时,保温10min(升温速率为5℃/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250℃后(升温速率为5℃/s),再将温度缓慢地升至380℃(升温速率为5℃/min),之后再快速将温度升至550℃(升温速率为5℃/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,其中磁控溅射条件为衬底温度500℃,溅射功率为60W,通入氩气前真空度为7×10-4Pa;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,其中所述的二次硫化热处理过程为先进行低温缓慢硫化热处理,再进行第二次高温快速硫化热处理,具体为快速升温至250℃,升温速率为5℃/s,再将温度缓慢升至380℃,升温速率为5℃/min,之后再快速将温度升至550℃,升温速率为5℃/s,保温10min,自然冷却。
2.根据权利要求1所述的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.根据权利要求1所述的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,二次硫化后的铜锌锡硫的光学带隙为1.52eV。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410326643.5A CN104282804B (zh) | 2014-09-03 | 2014-09-03 | 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 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201410326643.5A CN104282804B (zh) | 2014-09-03 | 2014-09-03 | 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 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104282804A CN104282804A (zh) | 2015-01-14 |
CN104282804B true CN104282804B (zh) | 2017-07-11 |
Family
ID=52257497
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410326643.5A Expired - Fee Related CN104282804B (zh) | 2014-09-03 | 2014-09-03 | 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 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104282804B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106653898B (zh) * | 2016-11-04 | 2019-06-11 | 苏州腾晖光伏技术有限公司 | 一种czts太阳能电池 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103219420A (zh) * | 2013-03-26 | 2013-07-24 | 无锡舒玛天科新能源技术有限公司 | 一种用四元素合金靶材制备铜锌锡硫薄膜的方法 |
CN103354252A (zh) * | 2013-07-17 | 2013-10-16 | 深圳先进技术研究院 | Czts太阳电池的pn结及czts太阳电池器件的制备方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011126454A1 (en) * | 2010-04-09 | 2011-10-13 | Platzer-Bjoerkman Charlotte | Thin film photovoltaic solar cells |
TWI435463B (zh) * | 2011-07-26 | 2014-04-21 | Au Optronics Corp | 形成光電轉換層之方法 |
-
2014
- 2014-09-03 CN CN201410326643.5A patent/CN104282804B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN103219420A (zh) * | 2013-03-26 | 2013-07-24 | 无锡舒玛天科新能源技术有限公司 | 一种用四元素合金靶材制备铜锌锡硫薄膜的方法 |
CN103354252A (zh) * | 2013-07-17 | 2013-10-16 | 深圳先进技术研究院 | Czts太阳电池的pn结及czts太阳电池器件的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN104282804A (zh) | 2015-01-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100511729C (zh) | 一种制备Cu2ZnSnS4半导体薄膜太阳能电池吸收层的工艺 | |
CN107871795B (zh) | 一种基于柔性钼衬底的镉掺杂铜锌锡硫硒薄膜的带隙梯度的调控方法 | |
CN102372302A (zh) | 铜锌锡硫或铜锌锡硒薄膜太阳能电池吸收层靶材及其制备方法和应用 | |
CN101101939A (zh) | 一种制备Cu2ZnSnS4薄膜太阳能电池吸收层的工艺 | |
CN102712996A (zh) | 溅射靶、化合物半导体薄膜、具有化合物半导体薄膜的太阳能电池以及化合物半导体薄膜的制造方法 | |
CN104947050B (zh) | 一种CZTSSe薄膜的硫化物靶材共溅射制备方法及产品 | |
CN105336800A (zh) | Cigs基薄膜太阳能电池光吸收层的制备方法 | |
CN106783541A (zh) | 一种硒化亚锗多晶薄膜和含有该薄膜的太阳能电池及其制备方法 | |
CN103088301B (zh) | 一种铜铟镓硒薄膜的硒化处理装置、方法及铜铟镓硒薄膜器件 | |
CN106549082B (zh) | 合金靶与硫化物靶共溅射制备铜锌锡硫薄膜吸收层的方法 | |
CN106449816B (zh) | 一种铜铟镓硒薄膜的制备方法 | |
CN104282804B (zh) | 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 | |
CN103985783B (zh) | 利用磁控溅射法在柔性衬底上制备铜锌锡硫薄膜的方法 | |
CN101805890A (zh) | 一种原位生长Cu2ZnSnS4光伏薄膜方法 | |
CN103219420B (zh) | 一种用四元素合金靶材制备铜锌锡硫薄膜的方法 | |
CN105118877B (zh) | 一种铜铟镓硫硒薄膜材料的制备方法 | |
CN106229362B (zh) | 一种铜铟镓硒薄膜制备方法及铜铟镓硒薄膜 | |
CN106449812B (zh) | 溅射锡靶和硫化铜靶制备铜锡硫薄膜电池的方法 | |
CN104404462B (zh) | 一种共溅射低温快速制备多晶硅薄膜的方法 | |
CN110349836A (zh) | 一种一定禁带宽度硒化亚锗薄膜的制备方法 | |
CN106637107A (zh) | 一种Se/S比连续可调的Cu2ZnSn(S1-xSex)4薄膜的制备方法 | |
CN104393096A (zh) | 一种禁带宽度可控的铜锌锡硫硒薄膜材料的制备方法 | |
CN104060235A (zh) | 一种通过硒元素掺杂提高铜镉锡硫薄膜晶粒尺寸的制备方法 | |
CN104934502A (zh) | 一种硒气压可控的铜铟镓硒薄膜硒化装置 | |
CN105633212B (zh) | 一种基于一步共蒸发工艺制备梯度带隙光吸收层的方法和装置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170711 Termination date: 20180903 |