CN105895735A - 氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 - Google Patents
氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 Download PDFInfo
- Publication number
- CN105895735A CN105895735A CN201610110324.XA CN201610110324A CN105895735A CN 105895735 A CN105895735 A CN 105895735A CN 201610110324 A CN201610110324 A CN 201610110324A CN 105895735 A CN105895735 A CN 105895735A
- Authority
- CN
- China
- Prior art keywords
- zinc
- copper
- tin
- sulfur
- layer
- 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.)
- Pending
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 50
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000004544 sputter deposition Methods 0.000 title claims abstract description 35
- 239000010409 thin film Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- YADHPPSCECSOLO-UHFFFAOYSA-N [Sn]=O.[Zn].[Cu] Chemical compound [Sn]=O.[Zn].[Cu] YADHPPSCECSOLO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 239000005361 soda-lime glass Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010521 absorption reaction Methods 0.000 claims abstract description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 63
- 238000002360 preparation method Methods 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000010439 graphite Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical compound [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 claims description 3
- 238000005486 sulfidation Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- OEDMOCYNWLHUDP-UHFFFAOYSA-N bromomethanol Chemical compound OCBr OEDMOCYNWLHUDP-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000011135 tin Substances 0.000 claims 1
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 4
- 238000005987 sulfurization reaction Methods 0.000 abstract description 3
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 229910052733 gallium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 238000000137 annealing Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910004613 CdTe Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000701 toxic element Toxicity 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
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明公开了一种制备铜锌锡硫薄膜电池的方法,具体包括以下步骤:将钠钙玻璃衬底用丙酮、酒精、去离子水超声清洗,用重铬酸钾溶液浸泡,最后用去离子水超声清洗,用氮气吹干备用。将钠钙玻璃衬底放入磁控溅射系统中沉积1μm的钼背电极;以SLG/Mo/ZnO/Sn/Cu的顺序进行射频溅射,沉积600~800nm的铜锌锡氧预制层。将预制层在氮气下低温热处理,随后高温硫化得到铜锌锡硫薄膜吸收层,并制备成完整的电池结构。本发明的优点在于:(1)铜锌锡预制层在硫化后很难生成平坦吸收层,铜锌锡氧预制层硫化后表面平整并且没有针孔。(2)引入氧原子避免了硫化过程中体积突然膨胀,使薄膜脱落。(3)氧化锌在底部能起到阻挡层的作用,抑制硫化过程中生成硫化钼。
Description
技术领域
本发明涉及一种用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法,用于制备薄膜太阳电池,属于光电材料新能源技术领域。
背景技术
目前,无毒、环境友好和原材料丰富的薄膜材料成为光伏领域的研究热点。基于Cu(In,Ga)Se2(CIGS)和CdTe的薄膜太阳电池虽然已经商业化,但由于组成元素中Se和Cd有毒,而In、Ga和Te属于稀缺元素,在自然界中的含量分别为In: 0.05ppm, Ga: 0.04ppm, Te:0.009ppm,基于此制约着他们进一步大规模的生产。而对于新型四元化合物半导体Cu2ZnSnS4(CZTS),组成CZTS的四种素中不仅不含有毒元素和稀贵元素,而且四中元素在自然界中的含量很丰富,Cu: 50ppm, Zn: 75ppm, Sn: 2.2ppm, S: 260ppm,相对于In、Ga和Te非常丰富,且Zn、Sn和S的价格远远低于Ga和Se等元素。CZTS具有稳定的锌黄锡矿结构,是一种Ⅰ2-Ⅱ-Ⅳ-Ⅵ4族p型半导体材料,它以锡和锌替代铜铟镓硒中的镓和铟,以硫替代硒而构成。作为直接带隙半导体材料CZTS的禁带宽度为1.4~1.5 eV,接近单节太阳电池所需的最佳带隙宽度(1.45 eV),此外,该材料的吸收系数大于104 cm-1。基于此,CZTS薄膜的太阳电池其理论效率可达32.2 %,是一种有替代Cu(In,Ga)Se2(CIGS)和CdTe的新型薄膜太阳电池。
目前制备CZTS薄膜的方法主要有磁控溅射法,热蒸发法,脉冲激光沉积,溶胶凝胶法,电化学法,喷雾热解法,旋涂法等。而基于磁控溅射化合物靶制备CZTS的相对较少,2013年日本丰田研发中心分步溅射ZnS-Sn-Cu后在H2S气氛下硫化制备出7.6 %的纯CZTS薄膜太阳电池,7.6 %的效率也是目前磁控溅射纯CZTS薄膜太阳电池之最。而世界纪录纯的CZTS薄膜吸收层的太阳电池的效率为8.4%,由IBM用共蒸发法制备,同时IBM用涂覆法制备的基于CZTSSe薄膜吸收层的太阳电池效率达到12.6%,也为世界之最,虽然如此,基于CZTS薄膜吸收层的太阳电池效率距离32.2 %的理论效率还有很大的差距。本发明简化工艺步骤、降低生产成本、制备出成分可控的铜锌锡硫薄膜吸收层,且易于大规模生产,有利于该材料在薄膜太阳能电池工业中的推广与应用。
发明内容
有鉴于现有技术的上述缺陷,本发明所要解决的技术问题是提供一种工艺简便、成分可控、工艺流程短和可重现性好的制备方法,制备出贫铜富锌的铜锌锡硫薄膜电池。
本发明所涉及的一种铜锌锡硫薄膜电池的制备方法按以下步骤实施:
(1)衬底清洗:将钠钙玻璃依次用去污粉、丙酮、酒精、去离子水超声清洗、重铬酸钾溶液浸泡24h,用去离子水超声清洗浸泡过重铬酸钾溶液的钠钙玻璃,用I号液和II号液处理衬底,再用去离子水清洗,并用氮气吹干备用;
(2)将清洗好的钠钙玻璃放入磁控溅射系统里,在室温不同压强下,在钠钙玻璃上沉积1μm的双层钼背电极薄膜;
(3)铜锌锡氧预制层的制备:利用磁控溅射系统,按照SLG/ Mo/ ZnO/ Sn/ Cu的顺序进行射频溅射,沉积600~800nm的铜锌锡氧薄膜预制层;
(4)铜锌锡硫薄膜吸收层的制备:将步骤3)所制备的铜锌锡氧薄膜预制层在氮气或氩气保护下260℃热处理30 min,随后将热处理过的预置层与硫粉一起放入石墨舟,最后将石墨舟放入硫化炉中,以20-30℃ /min 升温速率加热硫化炉,从室温升到 560 - 580℃,维持 8-15 min,自然冷却至室温后得到铜锌锡硫薄膜吸收层。硫化过程中氧原子很容易被硫原子替代,所以硫化后得到的是铜锌锡硫吸收层,含有少量氧原子。
(5)铜锌锡硫薄膜太阳电池的制备:将步骤4)所制备的铜锌锡硫薄膜吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相。把处理后的吸收层用化学水浴沉积CdS薄膜。然后再将水浴后的薄膜放入磁控溅射系统中射频沉积ZnO和ITO薄膜。接着用蒸发制备Ni/Al电极,最后将整个器件在快速退火炉中退火。
本发明采用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法中如步骤(1)所述衬底需在重铬酸钾溶液浸泡24h。
本发明采用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法中如步骤(2)所述将钠钙玻璃放入磁控溅射系统里,在室温不同压强下,在钠钙玻璃上沉积1μm的双层钼背电极薄膜;
本发明采用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法中如步骤(3)铜锌锡氧预制层的制备:利用磁控溅射系统,按照SLG/ ZnO/ Sn/ Cu的顺序进行射频溅射,沉积600~800nm的铜锌锡氧薄膜预制层;
本发明采用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法中如步骤(4)铜锌锡硫薄膜吸收层的制备:将制备的铜锌锡氧薄膜预制层在氮气或氩气保护下260℃热处理30min,随后将热处理过的预置层与硫粉一起放入石墨舟,最后将石墨舟放入硫化炉中,以20-30℃/min 升温速率加热硫化炉,从室温升到 560 - 580℃,维持 8-15 min,自然冷却至室温后得到铜锌锡硫薄膜吸收层。硫化过程中氧原子很容易被硫原子替代,所以硫化后得到的是铜锌锡硫吸收层,含有少量氧原子。
本发明采用氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法中如步骤(5)铜锌锡硫薄膜电池的制备:将制备好的铜锌锡硫薄膜吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相。把处理后的吸收层用化学水浴沉积CdS薄膜。然后再将水浴后的薄膜放入磁控溅射系统中射频沉积ZnO和ITO薄膜。接着用蒸发制备Ni/Al电极,最后将整个器件在快速退火炉中退火。
附图说明
图1为实施例1所制备的铜锌锡硫薄膜吸收层的XRD图
图2为实施例1所制备的铜锌锡硫薄膜吸收层的Raman图
图3为实施例1所制备的铜锌锡硫薄膜吸收层的SEM图
图4为实施例1所制备的电池效率I-V图
图5为实施例2所制备的铜锌锡硫薄膜吸收层的XRD图
图6为实施例2所制备的铜锌锡硫薄膜吸收层的Raman图
图7为实施例2所制备的铜锌锡硫薄膜吸收层的SEM图
图8为实施例2所制备的电池效率I-V图。
具体实施方式
实施例1
(1)衬底清洗:将钠钙玻璃依次用去污粉、丙酮、酒精、去离子水超声清洗、重铬酸钾溶液浸泡24小时,用I号液和II号液处理衬底,再用去离子水清洗,并用氮气吹干备用;
(2)将清洗好的钠钙玻璃放入磁控溅射系统里,以尺寸为76.2mm*3mm的钼靶作为靶材进行直流溅射,本底真空为5.0*10-4pa,起辉气压为1.6pa,功率为200W,在氩气为1.6pa时溅射20min,随后调节氩气为0.3pa溅射50min,按上述要求操作在钠钙玻璃上得到1μm的钼背电极薄膜;
(3)铜锌锡氧薄膜预置层的制备:以尺寸为76.2mm*3mm的ZnO靶、Sn靶、Cu靶作为靶材进行射频溅射,本底真空为5.0*10-4pa,衬底温度为室温,起辉气压为1.6pa,功率和沉积时间分别为ZnO 50W 124min、Sn 50W 32min、Cu 100W 17min10s,工作压强为0.3pa,按上述要求操作在步骤(2)的基础上得到 780nm的铜锌锡氧薄膜预置层。
(4)铜锌锡硫薄膜吸收层的制备:将步骤(3)所制备的铜锌锡氧薄膜预置层与0.5克硫粉和0.02克锡粉放入石墨舟,随后将石墨舟放入退火炉中在氮气保护下升温至580℃进行8min的退火处理,自然冷却至室温将样品取出得到铜锌锡硫薄膜吸收层。
(5)铜锌锡硫薄膜电池的制备:将步骤(4)所制备的铜锌锡硫吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相。把处理后的吸收层用化学水浴沉积60nm的CdS薄膜。然后再将水浴后的薄膜放入磁控溅射系统中射频溅射50nm的本征ZnO和400nm的ITO,功率分别为25W和50W。本底真空为5.0*10-4pa,衬底温度为室温,工作气压为0.5pa;接着在蒸发制备2μm的Ni/Al电极,最后将整个器件在快速退火炉中220℃处理20min。
实施例2
(1)衬底清洗:将钠钙玻璃依次用去污粉、丙酮、酒精、去离子水超声清洗、重铬酸钾溶液浸泡24小时,用I号液和II号液处理衬底,再用去离子水清洗,并用氮气吹干备用;
(2)将清洗好的钠钙玻璃放入磁控溅射系统里,以尺寸为76.2mm*3mm的钼靶作为靶材进行直流溅射,本底真空为5.0*10-4pa,起辉气压为1.6pa,功率为200W,在氩气为1.6pa时溅射20min,随后调节氩气为0.3pa溅射50min,按上述要求操作在钠钙玻璃上得到1μm的钼背电极薄膜;
(3)铜锌锡氧薄膜预置层的制备:以尺寸为76.2mm*3mm的ZnO靶、Sn靶、Cu靶作为靶材进行射频溅射,本底真空为5.0*10-4pa,衬底温度为室温,起辉气压为1.6pa,功率和沉积时间分别为ZnO 50W 124min、Sn 50W 31min、Cu 100W 16min35s,工作压强为0.3pa,按上述要求操作在步骤(2)的基础上得到 760nm的铜锌锡氧薄膜预置层。
(4)铜锌锡硫薄膜吸收层的制备:将步骤(3)所制备的铜锌锡氧薄膜预置层与0.5克硫粉和0.02克锡粉放入石墨舟,随后将石墨舟放入退火炉中在氮气保护下升温至580℃进行15min的退火处理,自然冷却至室温将样品取出得到铜锌锡硫薄膜吸收层。
(5)铜锌锡硫薄膜电池的制备:将步骤(4)所制备的铜锌锡硫吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相。把处理后的吸收层用化学水浴沉积60nm的CdS薄膜。然后再将水浴后的薄膜放入磁控溅射系统中射频溅射50nm的本征ZnO和400nm的ITO,功率分别为25W和50W。本底真空为5.0*10-4pa,衬底温度为室温,工作气压为0.5pa;接着在蒸发制备2μm的Ni/Al电极,最后将整个器件在快速退火炉中220℃处理20min。
Claims (6)
1.氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法,其特征在于,包括以下步骤:第一步衬底清洗:将钠钙玻璃依次用去污粉、丙酮、酒精、去离子水超声清洗、重铬酸钾溶液浸泡24h,用去离子水超声清洗浸泡过重铬酸钾溶液的钠钙玻璃,用I号液和II号液处理衬底,再用去离子水清洗,并用氮气吹干备用;第二步将清洗好的钠钙玻璃放入磁控溅射系统里,在室温不同压强下,在钠钙玻璃上沉积1μm的双层钼背电极薄膜;第三步铜锌锡氧预制层的制备:利用磁控溅射系统,按照SLG/ Mo/ ZnO/ Sn/ Cu的顺序进行射频溅射,沉积600~800nm的铜锌锡氧薄膜预制层;第四步铜锌锡硫薄膜吸收层的制备:将第三步所制备的铜锌锡氧薄膜预制层在氮气或氩气保护下260℃热处理30 min,随后将热处理过的预置层与硫粉一起放入石墨舟,最后将石墨舟放入硫化炉中,以20-30℃/min 升温速率加热硫化炉,从室温升到 560 - 580℃,维持 8-15 min,自然冷却至室温后得到铜锌锡硫薄膜吸收层,硫化过程中氧原子很容易被硫原子替代,所以硫化后得到的是铜锌锡硫吸收层,含有少量氧原子,第五步铜锌锡硫薄膜太阳电池的制备:将第四步所制备的铜锌锡硫薄膜吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相,把处理后的吸收层用化学水浴沉积CdS薄膜,然后再将水浴后的薄膜放入磁控溅射系统中射频沉积ZnO和ITO薄膜,接着用蒸发制备Ni/Al电极,最后将整个器件在快速退火炉中退火。
2.如权利要求1所述的氧化锌靶溅射制备铜锌锡硫薄膜电池的制备方法,其特征在于所述的衬底需在重铬酸钾溶液浸泡24 h。
3.如权利要求1所述的氧化锌靶溅射制备铜锌锡硫薄膜电池的方法,其特征在于所述的铜锌锡氧薄膜预制层中,预置层厚度设计为600~800nm;Cu、Zn和Sn摩尔原子比设计为:Cu/Zn+Sn=0.58;Zn/Sn=1.47。
4.如权利要求1所述的一种铜锌锡硫薄膜电池的制备方法,其特征在于所述第四步铜锌锡氧薄膜预制层在氮气或氩气保护下260℃热处理30min。
5.如权利要求1所述的一种铜锌锡硫薄膜电池的制备方法,其特征在于所述第四步将热处理过的预置层与硫粉一起放入石墨舟,最后将石墨舟放入硫化炉中,以 20 ~30℃ /min 升温速率加热硫化炉,从室温升到 560 ~ 580℃,维持 8~15 min,自然冷却至室温后得到铜锌锡硫薄膜吸收层,硫化过程中氧原子很容易被硫原子替代,所以硫化后得到的是铜锌锡硫吸收层,含有少量氧原子。
6.如权利要求1所述的一种铜锌锡硫薄膜电池的制备方法,其特征在于所述第五步所制备的铜锌锡硫薄膜吸收层用盐酸、溴-甲醇溶液进行刻蚀,以便除去吸收层表面ZnS和Cu2SnS3等二次相,最后将整个器件在快速退火炉中退火。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610110324.XA CN105895735A (zh) | 2016-02-29 | 2016-02-29 | 氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610110324.XA CN105895735A (zh) | 2016-02-29 | 2016-02-29 | 氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN105895735A true CN105895735A (zh) | 2016-08-24 |
Family
ID=57013794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610110324.XA Pending CN105895735A (zh) | 2016-02-29 | 2016-02-29 | 氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105895735A (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107086251A (zh) * | 2017-04-19 | 2017-08-22 | 河北大学 | 一种刻蚀铜锌锡硫薄膜表面二次相的方法 |
CN108231925A (zh) * | 2017-12-01 | 2018-06-29 | 南京邮电大学 | 一种高效cis/cigs太阳能电池的制备方法 |
CN110660589A (zh) * | 2019-10-09 | 2020-01-07 | 温州大学 | 硫化亚铜薄层对电极的制备及应用 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102800747A (zh) * | 2012-07-11 | 2012-11-28 | 上海大学 | 一种ZnS包覆的ZnO纳米阵列核壳结构的制备方法 |
CN103390674A (zh) * | 2013-07-17 | 2013-11-13 | 深圳先进技术研究院 | Czts柔性太阳电池及其制备方法 |
CN103474487A (zh) * | 2013-09-02 | 2013-12-25 | 深圳先进技术研究院 | 铜锌锡硫太阳能电池器件及其制备方法 |
US20140287551A1 (en) * | 2008-10-01 | 2014-09-25 | Stion Corporation | Thermal pre-treatment process for soda lime glass substrate for thin film photovoltaic materials |
CN104409535A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种铜锌锡硫薄膜太阳电池器件及其制备方法 |
CN104409559A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种铜锌锡硫薄膜太阳电池器件及其制备方法 |
CN104779318A (zh) * | 2014-01-13 | 2015-07-15 | 东莞日阵薄膜光伏技术有限公司 | 低温溅射铜锌锡硒太阳能电池 |
-
2016
- 2016-02-29 CN CN201610110324.XA patent/CN105895735A/zh active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140287551A1 (en) * | 2008-10-01 | 2014-09-25 | Stion Corporation | Thermal pre-treatment process for soda lime glass substrate for thin film photovoltaic materials |
CN102800747A (zh) * | 2012-07-11 | 2012-11-28 | 上海大学 | 一种ZnS包覆的ZnO纳米阵列核壳结构的制备方法 |
CN103390674A (zh) * | 2013-07-17 | 2013-11-13 | 深圳先进技术研究院 | Czts柔性太阳电池及其制备方法 |
CN103474487A (zh) * | 2013-09-02 | 2013-12-25 | 深圳先进技术研究院 | 铜锌锡硫太阳能电池器件及其制备方法 |
CN104779318A (zh) * | 2014-01-13 | 2015-07-15 | 东莞日阵薄膜光伏技术有限公司 | 低温溅射铜锌锡硒太阳能电池 |
CN104409535A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种铜锌锡硫薄膜太阳电池器件及其制备方法 |
CN104409559A (zh) * | 2014-09-30 | 2015-03-11 | 天津理工大学 | 一种铜锌锡硫薄膜太阳电池器件及其制备方法 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107086251A (zh) * | 2017-04-19 | 2017-08-22 | 河北大学 | 一种刻蚀铜锌锡硫薄膜表面二次相的方法 |
CN107086251B (zh) * | 2017-04-19 | 2019-02-15 | 河北大学 | 一种刻蚀铜锌锡硫薄膜表面二次相的方法 |
CN108231925A (zh) * | 2017-12-01 | 2018-06-29 | 南京邮电大学 | 一种高效cis/cigs太阳能电池的制备方法 |
WO2019105152A1 (zh) * | 2017-12-01 | 2019-06-06 | 南京邮电大学 | 一种高效cis/cigs太阳能电池的制备方法 |
CN110660589A (zh) * | 2019-10-09 | 2020-01-07 | 温州大学 | 硫化亚铜薄层对电极的制备及应用 |
CN110660589B (zh) * | 2019-10-09 | 2021-04-27 | 温州大学 | 硫化亚铜薄层对电极的制备及应用 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
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 | |
CN102034898B (zh) | 一种太阳电池用铜铟硫光电薄膜材料的制备方法 | |
CN106917068B (zh) | 基于磁控溅射和后硒化制备太阳能电池吸收层Sb2Se3薄膜的方法 | |
CN107623046B (zh) | 铜铟镓硒吸收层后处理方法及基于其的太阳电池制备方法 | |
CN105742412A (zh) | 一种薄膜太阳能电池吸收层碱金属掺入方法 | |
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 | |
CN104143579A (zh) | 一种锑基化合物薄膜太阳能电池及其制备方法 | |
CN113078239B (zh) | 一种硒化锑薄膜太阳电池及其制备方法 | |
CN102270699A (zh) | 无镉铜铟镓硒薄膜太阳能电池及其硫化锌缓冲层薄膜的制备方法 | |
CN109148641A (zh) | 铜锌锡硫硒薄膜太阳能电池及其制备方法和背电极的修饰方法 | |
CN107829071B (zh) | 铜锑硫薄膜材料的制备方法 | |
CN105895735A (zh) | 氧化锌靶溅射制备铜锌锡硫薄膜太阳电池的方法 | |
US20170207362A1 (en) | Method for forming thin film having sulfide single-crystal nanoparticles | |
CN105161572B (zh) | 一种铜锌锡硫太阳电池吸收层的墨水多层涂敷制备方法 | |
CN107134507B (zh) | 具有梯度成分太阳能电池吸收层铜铟硫硒薄膜的制备方法 | |
CN103602982A (zh) | 铜铟镓硫硒薄膜太阳电池光吸收层的非真空制备方法 | |
CN112259620A (zh) | 一种Sb2Se3薄膜太阳能电池及其制备方法 | |
CN109671803A (zh) | 一种薄膜太阳能电池制备方法 | |
CN104051577A (zh) | 提高太阳电池吸收层铜锌锡硫薄膜结晶性能的制备方法 | |
CN104716229A (zh) | 铜锌锡硒薄膜太阳电池的制备方法 | |
CN106374012A (zh) | 一种简单结构制备铜锌锡硫薄膜太阳电池的方法 | |
CN113078224A (zh) | 透明导电玻璃铜铟硒薄膜太阳能电池器件及其制备方法与应用 | |
CN112736150A (zh) | 一种铜铟镓硒薄膜太阳能电池及其制备方法 | |
CN106024976A (zh) | 一种由氯化铜制备铜镓硫光电薄膜的方法 | |
CN105428212A (zh) | 单靶溅射制备铜锌锡硒薄膜吸收层的方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160824 |