CN106067489A - 一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法 - Google Patents
一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法 Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 38
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 25
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 15
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229940084478 ganite Drugs 0.000 title claims abstract description 10
- 239000010409 thin film Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 239000010408 film Substances 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 11
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000005357 flat glass Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000000873 masking effect Effects 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052733 gallium Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 241000530268 Lycaena heteronea Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- JWYFRSAIWSROES-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].[SeH2] Chemical compound [O-2].[O-2].[Ti+4].[SeH2] JWYFRSAIWSROES-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 230000009466 transformation Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- 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
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Abstract
一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，属于太阳电池用光电薄膜制备技术领域，本发明通过如下步骤得到，首先清洗玻璃基片，然后将氯化铜、水合硝酸镓、二氧化硒放入溶剂中，并调整 pH值为4.0～7.0，用旋涂法在玻璃片上得到前驱体薄膜，烘干，放入有水合联氨的可密闭容器，使前驱体薄膜样品不与联氨接触，并将装有样品的密闭容器装入烘箱进行加热和保温处理，最后取出样品进行干燥，得到铜镓硒光电薄膜。本发明不需要高温高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜镓硒光电薄膜有较好的连续性和均匀性，主相为铜镓硒相，这种新工艺容易控制目标产物的成分和结构，为制备高性能的铜镓硒光电薄膜提供了一种成本低、可实现工业化的生产方法。
Description
技术领域
本发明属于太阳电池用光电薄膜制备技术领域，尤其涉及一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法。
背景技术
进入21世纪以来，能源和环境问题成为人们更加关注的热点，面对能源枯竭以及传统能源带来的环境污染，人们开始逐步寻找可以代替传统化石能源的新型能源新一轮的能源革命正在缓慢拉开序幕。光伏发电具有安全可靠、无噪声、无污染、制约少、故障率低、维护简便等优点，可以利用太阳能这种清洁、安全和环保的可再生能源，因此近几十年来太阳电池的研究和开发日益受到重视。
铜镓硒薄膜太阳电池目前可以认为是最有发展前景的薄膜电池之一，其光吸收层由低成本的铜基半导体材料组成，吸光能力远强于晶体硅，在太阳光谱区光吸收深度在微米量级。铜镓硒的光吸收系数高达105cm-1，明显高于Si和CdTe等太阳能电池材料，因此非常适合做光吸收材料。此外，铜镓硒还有一系列的有点：（1）铜镓硒是直接带隙半导体，这可减少对少数载流子扩散的要求；（2）在室温下铜镓硒带隙可调，随着镓含量的变化，其带隙可以在1.04～1.67eV范围内连续变化；（3）铜镓硒吸收系数很大，转换效率高，性能稳定，薄膜厚度小，约2μm，并且原料的价格较低，大面积制备时价格较低；（4）在较宽成分范围内电阻率都较小；（5）抗辐射能力强，没有光致衰减效应，因而使用寿命长；（6） P型铜镓硒材料的晶格结构与电子亲和力都能跟普通的N型窗口材料（如CdS、ZnO）匹配。
目前铜镓硒的制备方法主要有溶剂热法、喷射热解法（Spray Prolysis）、电喷射法、电沉积、化学沉积法、封闭的化学气相输运法、化学气相沉积、分子束外延、反应溅射法、真空蒸发法、有机金属化学气相沉积法、等。由于铜镓硒原料成本低，且其带隙可以随着镓含量而改变，从而提高光电转换效率，因此是一种非常有发展前途的太阳能电池材料，但现有工艺路线复杂、制备成本高，因而同样需要探索低成本的制备工艺。
象前面所述方法一样，其它方法也有不同的缺陷。与本发明相关的还有如下文献：
[1] Zheng Ping ping, Ding Tie zhu, Kang Zhen feng,Liu Wen de, Prearationof Intermediate Band Semiconductor Materials CuGaSe2:Ge. Journal of SyntheticCrystals Vol.43 No.8 (2014)1921-1925.
主要描述了采用脉冲激光沉积法在钙钠玻璃衬底上制备CuGaSe2:Ge薄膜，并且用X射线衍射仪，扫描电子显微镜对薄膜进行了测试表征。
[2] LiZhang,QingHe,Jianping Xiao,Chuanming Xu,yuming Xue,YunSun,Study of Polycrystalline CuGaSe2 and CuGa3Se5 Thin Films Deposited by PVD. 15thInternational Photovoltaic Science and Engineering Conference (2005)1176-1177.
主要描述了利用PVD法，在Mo背底制备铜镓硒薄膜，并且对制备的铜镓硒薄膜成相以及形貌测试表征。
[3] Zhao Yan min, Xiao Wen, Li Wei, Yang Li, Qiao Zai xiang,Influence of Substrates on the Wide Band Gap CGS Thin Films. Journal ofSynthetic Crystals.Vol.42 No.12 (2013)2572-2575.
主要描述了用“三步法”共蒸发工艺，在不同的衬底上制备铜镓硒薄膜，并且通过对薄膜的成分、形貌、结构和电学性能的分析，得到衬底对制备铜镓硒薄膜的影响。
[4] Zhang Li, He Qing, Xu Chuan Ming, Xue Yu Ming, LI Chang Jian, Theeffect of composition on structural and electronic properties inpolycrystalline CuGaSe2 thin film. Chinese Physics B. Vol. 17, No. 8 (2008)3138-3142.
主要描述了共蒸发方法制备铜镓硒太阳能电池薄膜，并且分析了铜镓硒的薄膜的物相和形貌，并且对铜镓硒薄膜的电性能进行了表征。
发明内容
本发明为了解决现有技术的不足，而发明了一种与现有技术的制备方法完全不同的，一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法。
本发明采用旋涂-化学共还原法制备铜镓硒薄膜材料，采用钠钙玻璃为基片，以氯化铜、水合硝酸镓、二氧化硒为原料，以去离子水、乙二醇、乙醇胺、氨水或这四种原料的两种以上的混合物为溶剂，以氨水为辅助介质来调整溶液的pH值，按元素计量比先以旋涂法制备一定厚度的含铜镓硒的前驱体薄膜，以水合联氨为还原剂，在密闭容器内在较低温度下加热，使前驱体薄膜还原并发生合成反应得到目标产物。
本发明的具体制备方法包括如下顺序的步骤：
a.进行玻璃基片的清洗，将大小为20mm×20mm玻璃片放入按体积比硫酸：蒸馏水=2:1的溶液中，超声波清洗30min；再将玻璃片放入体积比丙酮：蒸馏水=5：1的溶液中，超声波清洗30min；再在蒸馏水中将玻璃基片用超声振荡30min；将上述得到的玻璃基片排放在玻璃皿中送入烘箱中，在100℃下烘干供制膜用。
b.将氯化铜、水合硝酸镓、二氧化硒放入溶剂中，使溶液中的物质均匀混合，并调节pH值。具体地说，可以将1.0～3.0份氯化铜、1.5～4.5份水合硝酸镓、1.2～3.6份二氧化硒放入110～450份的溶剂中，使溶液中的物质均匀混合,可加入100～250份氨水来调整溶液的pH值为4.0～7.0，其中溶剂为去离子水、乙二醇、乙醇胺、氨水中至少一种的混合溶液。
c.制作外部均匀涂抹步骤b所述溶液的基片，并烘干，得到前驱体薄膜样品。可以将上述溶液滴到放置在匀胶机上的玻璃基片上，再启动匀胶机以300～3500转/分旋转一定时间，使滴上的溶液涂均匀后，在100℃对基片进行烘干后，再次重复滴上前述溶液和旋转涂布后再烘干，如此重复5～15次，于是在玻璃基片上得到了一定厚度的前驱体薄膜样品。
d.将步骤c所得前驱体薄膜样品置于支架上，放入有水合联氨的可密闭容器，使前驱体薄膜样品不与联氨接触。水合联氨放入为35～40份。将装有前驱薄膜样品的密闭容器放入烘箱中，加热至160～220℃之间，保温时间为5～20小时，然后冷却到室温取出。
e.将步骤d所得物，使其常温自然干燥后，即得到铜镓硒光电薄膜。
本发明不需要高温高真空条件，对仪器设备要求低，生产成本低，生产效率高，易于操作。所得铜镓硒光电薄膜有较好的连续性和均匀性，主相为铜镓硒相，这种新工艺容易控制目标产物的成分和结构，为制备高性能的铜镓硒光电薄膜提供了一种成本低、可实现大规模的工业化生产。
具体实施方式
实施例1
a. 玻璃基片的清洗：如前所述进行清洗玻璃基片，基片大小为20mm×20mm。
b. 将1.5份氯化铜、 2.5份水合硝酸镓和1.7份二氧化硒放入378.07份去离子水中均匀混合， 加氨水至pH为4.5，利用超声波振动30min以上，使溶液中的物质均匀混合。
c. 将上述溶液滴到放置在匀胶机上的玻璃基片上，再启动匀胶机，匀胶机以300转/分转动5秒，以3000转/分旋转15秒，使滴上的溶液涂均匀后，在100℃对基片进行烘干后，再次重复滴上前述溶液和旋转涂布后再烘干，如此重复10次，于是在玻璃基片上得到了一定厚度的前驱体薄膜样品。
d.将上述工艺所得的前驱体薄膜样品放入可密闭的容器，并放入37.807份水合联氨，前驱薄膜样品置于支架上使其不与联氨接触。将装有前驱薄膜样品的密闭容器放入烘箱中，加热至200℃，保温时间10小时，然后冷却到室温取出。
e.将步骤d所得物，进行常温自然干燥，得到铜镓硒光电薄膜。
Claims (5)
1.一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，包括如下顺序的步骤：
a.玻璃基片的清洗；
b.将1.0～3.0份氯化铜、1.5～4.5份水合硝酸镓、1.2～3.6份二氧化硒放入110～450份的溶剂中，使溶液中的物质均匀混合，并调整pH值至4.0～7.0；
c.制作外部均匀涂抹步骤b所述溶液的基片，并烘干，得到前驱体薄膜样品；
d.将步骤c所得前驱体薄膜样品置于支架上，放入有水合联氨的可密闭容器，使前驱体薄膜样品不与联氨接触；将装有前驱薄膜样品的密闭容器放入烘箱中，加热至160～220℃之间，保温时间为5～20小时，然后冷却到室温取出；
e.将步骤d所得物，进行自然干燥，得到铜镓硒光电薄膜。
2.如权利要求1所述的一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，其特征在于，步骤a所述清洗，是将玻璃基片大小为20mm×20mm，放入按体积比硫酸：蒸馏水=2:1的溶液中，超声波清洗；再将玻璃片放入按体积比丙酮：蒸馏水=5：1的溶液中，超声波清洗；再在蒸馏水中将玻璃基片用超声振荡；将上述得到的玻璃基片排放在玻璃皿中送入烘箱中烘干供制膜用。
3.如权利要求1所述的一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，其特征在于，步骤b所述的溶剂为去离子水、乙醇、乙二醇、乙醇胺、氨水中至少一种。
4.如权利要求1所述的一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，其特征在于，步骤c所述均匀涂抹的基片，是通过匀胶机涂抹，匀胶机以300～3500转/分旋转，然后对基片进行烘干后，再次如此重复5～15次，得到了一定厚度的前驱体薄膜样品。
5.如权利要求1所述的一种由氯化铜和硝酸镓制备铜镓硒光电薄膜的方法，其特征在于，步骤d所述密闭容器内放入35～40份水合联氨。
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