CN105870000A - 铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法 - Google Patents

铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法 Download PDF

Info

Publication number
CN105870000A
CN105870000A CN201610410928.6A CN201610410928A CN105870000A CN 105870000 A CN105870000 A CN 105870000A CN 201610410928 A CN201610410928 A CN 201610410928A CN 105870000 A CN105870000 A CN 105870000A
Authority
CN
China
Prior art keywords
conversion layer
film
photoelectric absorption
inorganic agent
treating agent
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.)
Granted
Application number
CN201610410928.6A
Other languages
English (en)
Other versions
CN105870000B (zh
Inventor
陈良范
孙嵩泉
甄永泰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui Herze Cigs Technology Co Ltd
Original Assignee
Anhui Herze Cigs Technology Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Anhui Herze Cigs Technology Co Ltd filed Critical Anhui Herze Cigs Technology Co Ltd
Priority to CN201610410928.6A priority Critical patent/CN105870000B/zh
Publication of CN105870000A publication Critical patent/CN105870000A/zh
Application granted granted Critical
Publication of CN105870000B publication Critical patent/CN105870000B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02656—Special treatments
    • H01L21/02664—Aftertreatments
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • 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
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • 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
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂，它由以下组分混合组成：水、氢氧化钠、氢氧化钾、氯化铁、硫脲、氢氧化铵。其使用方法具有以下步骤：将所述的处理剂搅拌加热至40~90℃；将成膜有太阳能电池铜铟镓硒光电吸收转换层的衬底浸没至处理剂中20~60分钟，并不断摆动，以使薄膜周围的处理剂成分均匀；取出处理后的衬底，用去离子水反复冲洗至去离子水电阻值达10MΩ以上；用机械甩干的方式去除衬底上残留的水渍，在150℃烤箱内烘烤10分钟。利用本发明所提供的处理剂及使用方法对电吸收转换层处理后，抑制了薄膜中铜元素的析出以及表面铜元素与氧的反应，从而提高了转换效率并解决了薄膜老化现象。

Description

铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法
技术领域
本发明涉及半导体薄膜的处理技术，具体地说是一种铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法。
背景技术
铜铟镓硒薄膜太阳能电池是一种新型的高效薄膜太阳能电池。铜铟镓硒薄膜太阳能电池光电吸收转换层是由铜、铟、镓和硒四种元素组成的化合物半导体薄膜。该层铜铟镓硒化合物半导体薄膜对铜铟镓硒薄膜太阳能电池的效率有决定性影响，如何获得高质量的铜铟镓硒化合物半导体薄膜是有效提高铜铟镓硒薄膜太阳能电池转换效率的关键问题。同时，该层铜铟镓硒化合物半导体薄膜成膜后一般只能在空气环境中停留几个小时，如果停留时间过长将造成所谓的薄膜“老化”现象，最终严重影响到铜铟镓硒薄膜太阳能电池的光电转换效率，甚至造成整个电池的失效，铜铟镓硒化合物半导体薄膜的这一特性给大规模工业化生产造成了困难。目前没有较理想的对上述半导体薄膜的处理方法。
发明内容
本发明的目的在于提供一种铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法，使用该处理剂对成膜后的太阳能电池铜铟镓硒光电吸收转换层进行处理后，可有效提太阳能电池的效率，并解决了铜铟镓硒薄膜光电转换吸收层薄膜容易老化的问题。
为实现上述目的，本发明提供的处理剂采用以下方案：铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂，它由以下组分混合组成：水、氢氧化钠、氢氧化钾、氯化铁、硫脲、氢氧化铵，每升该处理剂中各组分的摩尔比为：氢氧化钠0.3~0.7M，氢氧化钾0.2~0.5M，氯化铁0.2~0.5M，硫脲0.5~1.0M，氢氧化铵0.7~1.5M，其余为水。
为实现上述目的，本发明提供的铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂的使用方法具有以下步骤：1、将所述的处理剂搅拌加热至40~90℃；2、将成膜有太阳能电池铜铟镓硒光电吸收转换层的衬底浸没至处理剂中20~60分钟，并不断摆动，以使薄膜周围的处理剂成分均匀；3、取出处理后的衬底，用去离子水反复冲洗至去离子水电阻值达10MΩ以上；4、用机械甩干的方式去除衬底上残留的水渍，在150℃烤箱内烘烤10分钟。
当铜铟镓硒光电吸收转换层成膜完成并暴露于空气中时，铜元素会在薄膜表面析出，并与空气中的氧气形成氧化铜和氧化亚铜等化合物，从而改变了薄膜表面的性质，形成缺陷，而铜元素的析出也改变了铜铟镓硒合金薄膜内部各元素的比例，进而造成了铜铟镓硒薄膜太阳能电池效率无法进一步提高，并带来薄膜老化现象，铜铟镓硒合金薄膜在空气中暴露时间越长则老化现象越严重。利用本发明所提供的处理剂及使用方法对铜铟镓硒光电吸收转换层处理后，抑制了薄膜中铜元素的析出以及表面铜元素与氧的反应，从而提高了转换效率并解决了薄膜老化现象。
本发明提供的处理剂所用原料获取容易、配制简单；本发明提供的方法步骤合理、操作方便。由本发明提供的处理剂及使用方法所获得的太阳能电池铜铟镓硒光电吸收转换层，具有光电吸收转换转换率高、抗老化能力强的特点。
附图说明
图1 为利用本发明处理和利用本发明处理之后的一组样品的I-V曲线测试对比图；
图2为利用本发明处理的一组样品的光电转换吸收层浓度随薄膜厚的变化对比图；
图3 为同一实验片上切分出的三个实验小片的填充因子和转换效率对比图。
具体实施方式
以下结合实施例及附图对本发明进一步说明。
本实施例提供的铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂，由以下组分混合组成：水、氢氧化钠、氢氧化钾、氯化铁、硫脲、氢氧化铵，每升该处理剂中各组分的摩尔比为：氢氧化钠0.5M，氢氧化钾0.35M，氯化铁0.35M，硫脲0.75M，氢氧化铵1。2M，其余为水。该处理剂的配置过程为：将上述组分原料均匀混合即成。
用上述处理剂处理成膜后的太阳能电池铜铟镓硒光电吸收转换层，具体步骤如下：
1、将所述的处理剂搅拌加热至60~70℃；
2、将成膜有太阳能电池铜铟镓硒光电吸收转换层的衬底浸没至处理剂中35~45分钟，并不断摆动，以使薄膜周围的处理剂成分均匀；
3、取出处理后的衬底，用去离子水反复冲洗至去离子水电阻值达10~11MΩ以上；
4、用机械甩干的方式去除衬底上残留的水渍，在150℃烤箱内烘烤10分钟。
由本发明处理后的太阳能电池铜铟镓硒光电吸收转换层通过以下测试或对比，可以看出所产生的效果。
1、图1给出了未利用本发明处理和利用本发明处理之后的一组样品的I-V曲线测试对比图，由图1可见，相对于未经处理的样品，经过本发明所述处理方法处理的样品的开路电压、短路电流密度、填充因子都有了大幅提高，并由此其转换效率从5.99%增加为9.27%。
2、图2给出了利用本发明处理的一组样品的光电吸收转换层掺杂浓度随薄膜厚的变化对比图，由图2可见，经处理后的样品其光电吸收转换层的掺杂浓度有了显著的增加。
3、图3给出了同一实验片上切分出的三个实验小片的填充因子（FF）和转换效率对比图，图3中，最左边数据显示的是未经处理的实验小片的结果，中间和右边数据显示的是经过本发明专利方法处理的实验小片的结果。由图3可见，相较于未经处理的样品，经过本发明专利所述方法处理后的样品的填充因子和转换效率都有了不同程度的提高。
另外，另外通过下表1所示实验数据可见，经过本发明专利所述方法、步骤处理的铜铟镓硒薄膜太阳能电池光电吸收转换层的“老化”现象得到了解决。最长97天暴露于空气中的铜铟镓硒薄膜在上述处理后未表现出常见的薄膜老化影响电池效率的现象。
表1
电池样品编号 CIGS成膜后放置天数 开路电压（mV） 填充因子（%） 短路电流（mA/cm2) 光电转换效率（%）
Z1730-5 0 543 70.1 33.4 12.7
Z1730-19 84 573 72.3 30.3 12.5
Z1730-27 91 557 70 33 12.9
Z1730-36 92 540 71.5 32.4 12.5
Z1730-41 97 542 70.3 32.7 12.4

Claims (2)

1.铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂，其特征在于它由以下组分混合组成：水、氢氧化钠、氢氧化钾、氯化铁、硫脲、氢氧化铵，每升该处理剂中各组分的摩尔比为：氢氧化钠0.3~0.7M，氢氧化钾0.2~0.5M，氯化铁0.2~0.5M，硫脲0.5~1.0M，氢氧化铵0.7~1.5M，其余为水。
2.权利要求1所述处理剂的使用方法，其特征在于具有以下步骤：a、将所述的处理剂搅拌加热至40~90℃；b、将成膜有太阳能电池铜铟镓硒光电吸收转换层的衬底浸没至处理剂中20~60分钟，并不断摆动，以使薄膜周围的处理剂成分均匀；c、取出处理后的衬底，用去离子水反复冲洗至去离子水电阻值达10MΩ以上；d、用机械甩干的方式去除衬底上残留的水渍，在150℃烤箱内烘烤10分钟。
CN201610410928.6A 2016-06-04 2016-06-04 太阳能电池光电吸收转换层成膜后处理剂及使用方法 Active CN105870000B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610410928.6A CN105870000B (zh) 2016-06-04 2016-06-04 太阳能电池光电吸收转换层成膜后处理剂及使用方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610410928.6A CN105870000B (zh) 2016-06-04 2016-06-04 太阳能电池光电吸收转换层成膜后处理剂及使用方法

Publications (2)

Publication Number Publication Date
CN105870000A true CN105870000A (zh) 2016-08-17
CN105870000B CN105870000B (zh) 2018-12-14

Family

ID=56650107

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610410928.6A Active CN105870000B (zh) 2016-06-04 2016-06-04 太阳能电池光电吸收转换层成膜后处理剂及使用方法

Country Status (1)

Country Link
CN (1) CN105870000B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107331730A (zh) * 2017-07-03 2017-11-07 浙江爱旭太阳能科技有限公司 管式perc太阳能电池的修复工艺及制备工艺

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011044382A1 (en) * 2009-10-07 2011-04-14 Reel Solar Incorporated Porous substrates for fabrication of thin film solar cells
US20140308774A1 (en) * 2010-10-01 2014-10-16 Stion Corporation Method and device for cadmium-free solar cells
CN105118883A (zh) * 2015-07-29 2015-12-02 南京汉能薄膜太阳能有限公司 一种低镉cigs基薄膜太阳能电池及其制备方法
US20160111566A1 (en) * 2014-10-20 2016-04-21 Tsmc Solar Ltd. Absorber surface modification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011044382A1 (en) * 2009-10-07 2011-04-14 Reel Solar Incorporated Porous substrates for fabrication of thin film solar cells
US20140308774A1 (en) * 2010-10-01 2014-10-16 Stion Corporation Method and device for cadmium-free solar cells
US20160111566A1 (en) * 2014-10-20 2016-04-21 Tsmc Solar Ltd. Absorber surface modification
CN105118883A (zh) * 2015-07-29 2015-12-02 南京汉能薄膜太阳能有限公司 一种低镉cigs基薄膜太阳能电池及其制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107331730A (zh) * 2017-07-03 2017-11-07 浙江爱旭太阳能科技有限公司 管式perc太阳能电池的修复工艺及制备工艺
CN107331730B (zh) * 2017-07-03 2019-04-23 浙江爱旭太阳能科技有限公司 管式perc太阳能电池的修复工艺及制备工艺

Also Published As

Publication number Publication date
CN105870000B (zh) 2018-12-14

Similar Documents

Publication Publication Date Title
CN107359246B (zh) 一种甲胺铅碘钙钛矿太阳能电池的制作方法
CN106298995A (zh) 一种银掺杂铜锌锡硫硒光吸收层薄膜材料及其在太阳能电池中的应用
Shin et al. Improvement of the cell performance in the ZnS/Cu (In, Ga) Se2 solar cells by the sputter deposition of a bilayer ZnO: Al film
CN102212885A (zh) 多晶硅太阳能电池片的制绒方法
CN109950404A (zh) 一种提高钙钛矿太阳能电池效率和湿热稳定性的方法
CN105280826A (zh) 一种双电子传输层的新型聚合物太阳能电池
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
CN102136372B (zh) 一种经离子注入处理的染料敏化太阳能电池及其制备方法
Li et al. Defects Passivation via Potassium Iodide Post‐Treatment for Antimony Selenosulfide Solar Cells with Improved Performance
CN108110068A (zh) 一种无铅钙钛矿太阳能电池及其制备方法
CN115881853B (zh) 一种太阳电池及其制备方法
CN112490315A (zh) 碲化镉太阳能电池及其制备方法
JP2017054917A (ja) 光電変換層及び光電変換層の製造方法
CN110634988B (zh) 一种削弱多晶硅太阳能电池光衰的方法
CN105870000A (zh) 铜铟镓硒薄膜太阳能电池光电吸收转换层成膜后的处理剂及使用方法
CN108511606B (zh) 一种高短路电流、高转化效率的钙钛矿太阳能电池制备方法及产品
CN102163549A (zh) 一种晶体硅镀膜后不良片的处理液及其处理方法
CN109524547A (zh) 一种新型无机空穴传输层材料的制备方法及其应用
CN101527261B (zh) 一种可改善硫族半导体薄膜性能的水热处理方法
CN103700767A (zh) 一种倒置结构的聚合物太阳能电池及其制备方法
CN108336177B (zh) 一种铜锌锡硫薄膜太阳能电池及其制备方法
CN104916714B (zh) 以La‑TiO2为电子传输层的有机光伏电池及其制备方法
CN105742409A (zh) 一种黑硅表面清洗方法及黑硅电池制备方法
CN107689272B (zh) 一种类石墨烯氮化碳改性Al掺杂ZnO透明导电薄膜的制备方法
CN102891208B (zh) 太阳能电池片制绒方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 233000 Room 403, building 2, incubation plant, University Science and Technology Park, Bengbu Economic Development Zone, Anhui

Applicant after: Anhui constant copper indium gallium selenium Technology Co., Ltd.

Address before: 233030 268 Tang He road, Bengbu, Anhui

Applicant before: ANHUI HERZE CIGS TECHNOLOGY CO., LTD.

GR01 Patent grant
GR01 Patent grant