CN103337555B - Preparation of selenium powder or a thin film solar cell for copper indium sulfur - Google Patents

Preparation of selenium powder or a thin film solar cell for copper indium sulfur Download PDF

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CN103337555B
CN103337555B CN 201310232391 CN201310232391A CN103337555B CN 103337555 B CN103337555 B CN 103337555B CN 201310232391 CN201310232391 CN 201310232391 CN 201310232391 A CN201310232391 A CN 201310232391A CN 103337555 B CN103337555 B CN 103337555B
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CN 201310232391
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CN103337555A (en )
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段学臣
段文杰
李历历
朱奕漪
蒋波
刘梓琪
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中南大学
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    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
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    • Y02P70/521Photovoltaic generators

Abstract

本发明公开了一种用于薄膜太阳能电池的铜铟硫硒粉体或薄膜的制备方法;该方法是先将氯化铜和氯化铟分散于有机溶剂中,超声分散后得到分散液;在所得分散液中加入硫化钠和硒粉后,搅拌均匀,得到混合液;再将所述混合液转移至反应釜中,定容、密封后反应,反应完成后,抽滤,将滤渣先后用去离子水和无水乙醇洗涤,真空干燥,得到CuIn(S,Se)2粉体;或者是将所述混合液移至反应釜中,再加入玻璃基底,定容、密封后,液相沉积,将沉积得到的玻璃基底先后用去离子水和无水乙醇洗涤,真空干燥,得到CuIn(S,Se)2薄膜;该方法采用的设备简单,生产成本低;生产的CuIn(S,Se)2粉体、薄膜性能优良,稳定性好,可实现工业化生产;并能通过控制S元素的含量,可以使得CuIn(S,Se)2的带隙在1.21~1.45eV之间连续可调。 The present invention discloses a method for preparing selenium powder or a thin film solar cell for copper indium sulfur; the process is first copper chloride and indium chloride dispersed in an organic solvent, after ultrasonic dispersion to obtain a dispersion; in the resulting dispersion was added selenium sulfide and stirred uniformly to obtain a mixture; then the mixture was transferred to the reaction vessel, the volume, the reaction was sealed, after the completion of the reaction, suction filtration, the residue rinsed successively washed with deionized water and absolute ethanol, and dried in vacuo to give CuIn (S, Se) 2 powder; or is moved to the kettle mixture, and then the glass substrate was added, volume after sealing, liquid deposition, the glass substrate obtained by depositing successively washed with deionized water and absolute ethanol, and dried in vacuo to give CuIn (S, Se) 2 thin film; simple equipment used in the process, low production cost; production of CuIn (S, Se) 2 powder, excellent film properties, good stability, industrial production; and by controlling the S content elements, may be such that CuIn (S, Se) 2, a band gap is continuously adjustable between 1.21 ~ 1.45eV.

Description

一种用于薄膜太阳能电池的铜铟硫砸粉体或薄膜的制备方法 A thin film copper indium sulfur drop for solar cell production method of a powder or film

技术领域 FIELD

[0001]本发明涉及一种用于薄膜太阳能电池的铜铟硫砸粉体或薄膜的制备方法,属于光电功能材料领域。 [0001] The present invention relates to a method for preparing copper indium thin-film solar cell of sulfur for the powder to drop or film, a photoelectric functional material belonging to the field.

背景技术 Background technique

[0002]能源是社会发展的动力,能源技术的革新带动人类社会日益进步。 [0002] Energy is the driving force of social development, energy technology innovations driven by the increasing progress of human society. 太阳能被认为是未来最有潜力的能源之一,而对于太阳能的利用主要是利用太阳能发电。 Solar energy is considered one of the most promising future, and for the use of solar energy is the use of solar power. 目前,太阳能电池已经发展到第二代——薄膜太阳能电池,其中的铜铟砸类(CIS、CIGS、CISSe等)薄膜太阳能电池因其光吸收系数高、光电转换效率好、性能稳定、无光致衰减现象、弱光发电性能好、抗辐照能力强等优点而备受各国科研机构及光伏企业的青睐。 Currently, solar cells have been developed to the second generation - thin film solar cell, wherein the copper-indium-based drop (CIS, CIGS, CISSe etc.) thin film solar cells because of their high light absorption coefficient, good photoelectric conversion efficiency, stable performance, matte induced attenuation phenomenon, good low-light power generation performance, strong anti-radiation ability, etc. has attracted national research institutes and solar companies of all ages.

[0003]铜铟砸类(CIS类)薄膜太阳能电池中,吸收层是影响电池光电转化效率的关键因素,为电池的核心材料。 [0003] type copper indium drop (CIS-based) thin film solar cell, the absorber layer is a key factor in cell conversion efficiency of the photoelectric effect is the core material of the battery. 目前,CIS类吸收层的制作方法可分为真空和非真空两类,真空类包括多元共蒸发法、磁控溅射后砸化法、离子束溅射沉积法等方法。 Currently, the production method of the CIS absorber layer can be divided into two types of vacuum and non-vacuum, vacuum-based polyol comprises a co-evaporation method, after the drop of a magnetron sputtering method, an ion-beam sputtering deposition. 专利CN101777604A报道了一种采用离子束溅射沉积法制备薄膜太阳能电池吸收层CuInSe2薄膜的方法,通过精确调整离子束溅射的参数等,先后溅射Cu、In和Se靶制备三元叠层或三元周期叠层薄膜,在同一高真空环境下,高温退火制备出CuInSe2薄膜。 Patent CN101777604A reported a method for ion beam sputter deposition method of thin film solar cell using a thin film CuInSe2 absorption layer, by ion beam sputtering precise adjustment of parameters and the like, has a sputtering Cu, In and Se or the laminate target prepared three yuan three yuan period laminated film, under the same high vacuum, high temperature annealing to prepare a CuInSe2 film. 真空工艺能够制备出光电转换效率较高的电池,所得电池产品具有一定优势,但由于真空设备需要很大的投资,制备条件苛刻、产率不高,成本较高,势必会影响到它的长久应用。 A vacuum process can be prepared in a higher photoelectric conversion efficiency of the battery, resulting battery products have certain advantages, but because of the large investment needed vacuum apparatus, harsh preparation conditions, the yield is not high, high cost, it will inevitably affect the long-term application.

[0004]目前,越来越多的研究者把目光投向低成本非真空工艺,如电沉积、丝网印刷法等。 [0004] Currently, more and more researchers to look toward a low-cost non-vacuum processes, such as electrodeposition, screen printing method. 非真空工艺虽然没有真空制备技术成熟,但其具有成本低、制备条件温和等优点,使其具有较大的研究开发前景。 Although non-vacuum process prepared without vacuum technology is mature, it has a low cost, mild preparation conditions, etc., it has a greater prospect of research and development.

[0005] 专利CN102683497A和专利CN101694854A分别报道了非真空湿化学法制备CuIn(S,Se)2薄膜的方法,与传统的高真空工艺相比,其工艺简单,成本较低,可操作性强,但后期仍需进行较为复杂的砸化退火处理。 [0005] Patents and patent CN102683497A CN101694854A reported the non-vacuum Wet Chemical Method CuIn (S, Se) 2 thin film method, compared with the conventional high vacuum process, which process is simple, low cost, easy to operate, but later still need to hit more complex annealing treatment.

[0006]因此需要研究一种新的制备CuIn(S,Se)2薄膜的非真空工艺来解决上述问题。 [0006] Thus the need for preparing a new study CuIn (S, Se) 2 thin film non-vacuum processes to solve the above problems.

发明内容 SUMMARY

[0007]本发明针对现有技术中的非真空工艺制备CuIn(S,Se)2薄膜的方法存在制备条件苛刻,热处理工艺复杂等缺陷,目的在于提供一种非真空制备CuIn(S,Se)2薄膜或粉体的方法,该方法采用的设备简单,原料廉价、生产成本低,工艺流程简单,无污染,易于实现工业化生产;制备出来的CuIn(S,Se)2薄膜或粉体光吸收特性佳,可以通过对S元素量的调控实现光吸收带的变化;特别是制备的CuIn(S,Se)2薄膜表面规整,薄膜附着力好、不易脱落,稳定性好。 [0007] The present invention resides harsh preparation conditions, defects such as complicated heat treatment process for preparing a non-film method prior art vacuum process CuIn (S, Se), aims to provide a non-vacuum preparing CuIn (S, Se) method 2 film or powder, the method uses a simple device, low cost of raw materials, production cost is low, the process is simple, clean and easy industrial production; CuIn (S, Se) 2 thin film was prepared out of the light-absorbing powder or good properties, change in the light absorption band by regulation of the amount of S element implemented; CuIn (S, Se) 2 prepared in particular structured film surface, good film adhesion, easy to fall off, good stability.

[0008]本发明提供了一种用于薄膜太阳能电池的铜铟硫砸粉体或薄膜的制备方法,该方法是先将氯化铜和氯化铟分散于有机溶剂中,超声分散后得到分散液;在所得分散液中加入硫化钠和砸粉后,搅拌均匀,得到混合液;再将所述混合液转移至反应釜中,定容、密封后,在160〜220°C下反应,反应完成后,抽滤,将滤渣先后用去离子水和乙醇洗涤,真空干燥,得到CuIn(S,Se)2粉体;或者是将所述混合液移至反应釜中,再加入玻璃基底,定容、密封后,在160〜220°C下液相沉积,将沉积得到的玻璃基底先后用去离子水和乙醇洗涤,真空干燥,得到CuIn(S,Se)2薄膜。 [0008] The present invention provides a method of preparing a copper indium thin-film solar cell of sulfur for the powder to drop or film, which is the first copper chloride and indium chloride dispersed in an organic solvent, a dispersion obtained after the ultrasonic dispersion solution; after addition of sodium sulfide powder and crushing the resulting dispersion was stirred uniformly to obtain a mixture; then the mixture was transferred to the reaction vessel, the volume, sealed, reacted at 160~220 ° C, the reaction after completion, suction filtered, the residue washed with deionized water and washed with ethanol and dried in vacuo to give CuIn (S, Se) 2 powder; or is moved to the kettle mixture, adding a glass substrate, a given receiving, after sealing, the liquid is deposited at 160~220 ° C, the glass substrate obtained by depositing successively washed with deionized water and ethanol and dried in vacuo to give CuIn (S, Se) 2 thin film.

[0009]上述方法中加入的硫化钠和砸粉中S和Se的摩尔关系满足S/(S+Se)=0.1〜0.9。 [0009] The method of adding sodium sulfide powder and smashing the molar relationship Se and S satisfy S / (S + Se) = 0.1~0.9.

[0010]上述方法中氯化铜和氯化铟与硫化钠和砸粉之间加入量满足理想化学计量比Cu:1n:(S+Se)=l〜1.05:1:2. [0010] The added amount satisfies the above process between the copper and indium chloride and the chloride and sodium sulfide powder drop over the stoichiometric ratio Cu: 1n: (S + Se) = l~1.05: 1: 2.

[0011] 所述的反应时间为12〜15h。 The reaction time according to [0011] of 12~15h.

[0012]所述的液相沉积的时间为12〜15h。 [0012] The liquid deposition time was 12~15h.

[0013]所述的有机溶剂为无水乙醇胺、无水乙二胺一种或两种。 [0013] The organic solvent is anhydrous ethanol amine, one or both of anhydrous ethylenediamine.

[0014] 所述的超声分散是在功率为200〜300W的超声下分散20〜60min。 [0014] The ultrasonic dispersion is dispersed in 20~60min 200~300W ultrasound power.

[0015] 所述的真空干燥是在60〜80°C下,真空干燥8〜12h。 The vacuum drying [0015] is at 60~80 ° C, and dried in vacuo 8~12h.

[0016]所述的玻璃基底为光学玻璃、钠钙玻璃、Mo玻璃或ITO透明导电玻璃;所述的玻璃基底规格约为25mm X 75mm的玻璃片。 [0016] The glass substrate is an optical glass, soda lime glass, Mo ITO transparent conductive glass or glass; said glass substrate of size about 25mm X 75mm glass.

[0017]所述的定容是添加无水乙醇胺或无水乙二胺到反应釜中,使反应釜中的混合溶液体积约占反应釜的75〜85%。 [0017] is the volume of anhydrous ethylenediamine or ethanolamine is added to the anhydrous reaction vessel, a mixed solution volume in the autoclave about 75~85% reaction kettle.

[0018]上述方法中反应后抽滤得到的滤渣先后用去离子水和无水乙醇分别反复洗涤直到洗涤后抽滤的滤液澄清、无明显漂浮物即可。 [0018] The residue obtained in filtration processes washed with deionized water and ethanol washing were repeated until the reaction after filtration the clear filtrate was washed, the float can no.

[0019]上述方法中沉积后所得的玻璃基底先后用去离子水和无水乙醇分别反复洗涤直到洗涤后的的洗液澄清、无明显漂浮物即可。 [0019] After the above process resulting in deposition of a glass substrate washed with deionized water and washed with ethanol until the washings is repeated after each washing clarification, no obvious to float.

[0020]本发明用于薄膜太阳能电池的铜铟硫砸粉体或薄膜的制备方法: [0020] Sulfur copper indium thin film solar cell of the present invention for the preparation of a powder or a drop film:

[0021] 1、先将氯化铜(CuCl2.2H20)、氯化铟(InCl3.4H20)按化学计量比I〜1.05:1分散于水乙醇胺或无水乙二胺中,然后在功率为200〜300W的超声下分散20〜60min得到分散液; [0021] 1, first copper (CuCl2.2H20) chloride, indium chloride (InCl3.4H20) stoichiometric I~1.05: 1 water-dispersible anhydrous ethylenediamine or ethanolamine, and then at a power of 200 ~300W the ultrasonic dispersion to obtain a dispersion 20~60min;

[0022] 2、然后按摩尔比3/(3+36)=0.1〜0.9加入硫化钠(他23.9H20)、砸粉(Se),搅拌均匀转移至反应釜得到混合液; [0022] 2, and a molar ratio of 3 / (3 + 36) = 0.1~0.9 was added sodium sulfide (he 23.9H20), hit powder (Se), transferred to the reaction vessel was stirred to give a uniform mixture;

[0023] 3、一方面直接将混合液转移至反应釜,再添加无水乙醇胺或无水乙二胺到反应釜中,使反应釜中的混合溶液体积约占反应釜的75〜85%、密封后在160〜220°C热处理12〜15h,抽滤,滤渣先后用去离子水、无水乙醇分别抽滤洗涤数次,再转移至真空干燥箱在60〜80°(3下真空干燥8〜1211,得到(]11111(5,56)2粉体; [0023] 3, on the one hand directly to the reaction mixture was transferred to a kettle was then dried over anhydrous anhydrous ethylenediamine or ethanolamine, to the reaction vessel, the volume of the mixed solution in the reaction vessel about 75~85% reaction kettle, after heat sealing at 160~220 ° C 12~15h, filtered off with suction, the filter cake washed with deionized water, filtered off with suction and washed several times with absolute ethanol, respectively, and transferred to a vacuum oven and dried at 60~80 ° (3 8 vacuo ~1211 give (] 11 111 (5,56) 2 powder;

[0024] 4、另一方面将混合液转移至反应釜中,再加入玻璃基底,在160〜220°C液相沉积12〜15h,然后将玻璃基底取出,先后用去离子水、无水乙醇分别洗涤数次,再转移至真空干燥箱在60〜80°C下真空干燥8〜12h,得到CuIn(S,Se)2薄膜。 [0024] 4, on the other hand the mixture was transferred to a reaction vessel, then added to a glass substrate, liquid-phase deposition at 160~220 ° C 12~15h, and then the glass substrate removed, washed with deionized water, ethanol was washed several times, then transferred to a vacuum oven and dried under vacuum at 60~80 ° C 8~12h, to give CuIn (S, Se) 2 thin film.

[0025]本发明的有益效果在于: [0025] Advantageous effects of the present invention:

[0026] 本发明选用CuCl2.2H20、InCl3.4H20、Na2S.9H20和Se粉作为反应原料,不涉及过于昂贵或具有毒性的有机金属盐类和砸化有机物,原料成本较低,对环境友好无污染; [0026] The present invention selects CuCl2.2H20, InCl3.4H20, Na2S.9H20 and Se powder as the starting material, does not involve too expensive or toxic organic and metal salts of organic drop, low raw material cost, environmentally friendly None Pollution;

[0027]本发明采用的设备简单,工艺流程短,无须复杂的砸化退火处理,操作简单,应用广泛,易于实现工业化生产; [0027] The present invention employs a simple, short process, without complex drop annealing treatment, simple, widely used, easy industrial production;

[0028]本发明制备的CuIn(S,Se)2粉体从图2可以看出,呈薄片簇状,厚度约为20nm,平均粒径在200nm左右,晶化程度尚,活性比表面积大,有利于提尚太阳光利用率; [0028] CuIn (S, Se) 2 powder prepared in the present invention can be seen from Figure 2, the sheet was tufted a thickness of about 20 nm, about 200 nm in average particle diameter, degree of crystallization still, active surface area, conducive to mention Shang Taiyang light utilization;

[0029]本发明制备的CuIn(S,Se)2薄膜从图3可以看出,表面规整,薄膜附着力好,不易脱落,稳定性好,光吸收特性佳,在紫外-可见光区均呈现出较强的吸收能力; [0029] CuIn (S, Se) 2 thin film prepared in the present invention can be seen from Figure 3, structured surface, good film adhesion, easy to fall off, good stability, good light absorption properties in the UV - visible region were shown strong absorption capacity;

[0030]本发明的制备方法通过控制各成分的初始摩尔比,可以实现对产物各元素成分的有效调控;随着S元素的增大,其光吸收性能出现“蓝移”现象,使其带隙可以在1.21-1.45eV连续可调。 [0030] The method of the present invention is prepared by controlling the initial molar ratio of the respective components, can achieve effective regulation of the elemental composition of the product; S elements with the increase of light absorption properties of a "blue shift" phenomenon, with it gap may be continuously adjustable 1.21-1.45eV.

附图说明 BRIEF DESCRIPTION

[0031]【图1】是本发明制备CuIn(S,Se)2粉体或薄膜的工艺流程图。 [0031] [FIG. 1] was prepared according to the present invention, CuIn (S, Se) 2 process flow diagram of a powder or a film.

[0032]【图2】是本发明实施例2中制备的CuIn(S,Se)2粉体的SEM图。 [0032] [Figure 2] is a CuIn (S, Se) 2 SEM image of the powder prepared in Example 2 of the embodiment of the present invention.

[0033]【图3】是本发明实施例3中制备的CuIn(S,Se)2薄膜的SEM图。 [0033] [FIG. 3] is a CuIn (S, Se) prepared in Example 3 of the present invention in the embodiment of FIG. 2 SEM film.

[0034]【图4】是不同S元素掺杂量下CuIn(S,Se)2粉体的光吸收曲线。 [0034] [4] FIG. S is different doping elements CuIn (S, Se) 2 powder light absorption amount in a graph.

[0035]【图5】是本发明实施例4中样品的光吸收曲线。 [0035] [5] is the light absorption curve of the sample in Example 4 of the present invention.

具体实施方式 detailed description

[0036]以下实施例旨在进一步说明本发明,而不是限制本发明。 [0036] The following examples are intended to further illustrate the present invention and not to limit the present invention.

[0037] 实施例1 [0037] Example 1

[0038] 称量:分别在电子分析天平(读数精度0.1mg)上称量0.8805g InCl3.4H20、 [0038] Weighing: respectively electronic analytical balance (reading accuracy 0.1 mg) was weighed 0.8805g InCl3.4H20 on,

0.5115g CuCl2.2H20,并将其转移至装有30mL乙醇胺的烧杯中,并用保鲜膜覆盖在其上面。 0.5115g CuCl2.2H20, and transferred to a beaker containing 30mL of ethanolamine, and covered with plastic wrap thereon.

[0039]分散:将烧杯放入超声分散机中,在功率为300W的超声下分散约30min得到分散液。 [0039] dispersion: The beaker was placed in an ultrasonic dispersion machine, is dispersed at a power of 300W ultrasound to obtain a dispersion of about 30min.

[0040] 定容:再分别在电子分析天平上称量0.2880g Na2S.9H20、0.3792g Se粉加入分散液中,搅拌均匀得到混合液;将分散后混合液转移入10mL反应釜中并用乙醇胺定容至反应釜容积的80%左右。 [0040] volume: then were weighed 0.2880g Na2S.9H20,0.3792g Se powder on an electronic analytical balance added to the dispersion and stirred to obtain a uniform mixture; After the dispersion mixture was transferred into a reaction vessel and treated with 10mL given ethanolamine volume to about 80% of the reactor volume.

[0041]热处理:将反应釜加盖后拧紧密封,放入恒温箱中于180°C反应15h。 [0041] Heat treatment: The reaction vessel capped screwed tightly sealed, placed into the reaction at 180 ° C incubator 15h.

[0042]抽滤洗涤:随炉冷却至室温之后,将反应产物先后用去离子水和无水乙醇分别真空抽滤洗涤数次,直至滤液澄清并且液面无明显漂浮物。 [0042] suction filtration and washed: After furnace cooling to room temperature, the reaction product was washed with deionized water, and vacuum filtration was washed with ethanol several times, until the filtrate was clear and no float level.

[0043]干燥取样:将滤纸放入培养皿或者烧杯中,至于真空干燥箱中70°C干燥12h得CuIn(S,Se)2 粉体。 [0043] The dried sample: the filter paper in a Petri dish or a beaker, as vacuum oven drying 70 ° C 12h to give CuIn (S, Se) 2 powder.

[0044] 实施例2 [0044] Example 2

[0045]称量:分别在电子分析天平上称量0.8805g InCl3.4H20、0.5115g CuCl2.2H20,将其转移至装约有30mL乙醇胺的烧杯中,并用保鲜膜覆盖在其上面。 [0045] Weighing: 0.8805g InCl3.4H20,0.5115g CuCl2.2H20 were weighed on an electronic analytical balance, transferred to a beaker fitted about 30mL of ethanolamine, and covered with plastic wrap thereon.

[0046]分散:将烧杯放入超声分散机中,在功率为300W的超声下分散约30min得到分散液。 [0046] The dispersion: The beaker was placed in an ultrasonic dispersion machine, is dispersed at a power of 300W ultrasound to obtain a dispersion of about 30min.

[0047] 定容:再分别在电子分析天平上称量0.7200g Na2S.9H20、0.2370g Se粉加入分散液中,搅拌均匀得到混合液;将分散后混合液转移入10mL反应釜中并用乙醇胺定容至反应釜容积的80%左右。 [0047] volume: then were weighed 0.7200g Na2S.9H20,0.2370g Se powder on an electronic analytical balance added to the dispersion and stirred to obtain a uniform mixture; After the dispersion mixture was transferred into a reaction vessel and treated with 10mL given ethanolamine volume to about 80% of the reactor volume.

[0048]热处理:将反应釜加盖后拧紧密封,放入恒温箱中于180°C反应15h。 [0048] Heat treatment: The reaction vessel capped screwed tightly sealed, placed into the reaction at 180 ° C incubator 15h.

[0049] 抽滤洗涤:随炉冷却至室温之后,将产物先后用去离子水和无水乙醇分别真空抽滤洗涤数次,直至滤液澄清并且液面无明显漂浮物。 [0049] The filtration was washed with: After furnace cooling to room temperature, the product was washed with deionized water, and vacuum filtration was washed with ethanol several times, until the filtrate was clear and no float level.

[0050]干燥取样:将滤纸放入培养皿或者烧杯中,至于真空干燥箱中80°C干燥Sh得CuIn(S,Se)2 粉体。 [0050] The dried sample: the filter paper in a Petri dish or a beaker, as 80 ° C in a vacuum oven and dried to give Sh CuIn (S, Se) 2 powder.

[0051 ] 实施例3 [0051] Example 3

[0052]称量:分别在电子分析天平上称量0.8805g InCl3.4H20、0.5115g CuCl2.2H20,并将其转移至装有30mL乙二胺的烧杯中,并用保鲜膜覆盖在其上面。 [0052] Weighing: 0.8805g InCl3.4H20,0.5115g CuCl2.2H20 were weighed on an electronic analytical balance and transferred to a beaker containing 30mL ethylenediamine, and covered with plastic wrap thereon.

[0053]分散:将烧杯放入超声分散机中,在功率300W的超声下分散约30min得到分散液。 [0053] The dispersion: The beaker was placed in an ultrasonic dispersing machine, at a power of 300W ultrasonic dispersion to obtain a dispersion of about 30min.

[0054] 定容:再分别在电子分析天平上称量1.1520g Na2S.9H20、0.0948g Se粉加入分散液中,搅拌均匀得到混合液;将分散后混合液转移入10mL反应釜中,同时加入规格为25mmX 75mm的ITO透明导电玻璃基底,并用乙醇胺定容至反应釜容积的80%左右。 [0054] volume: then were weighed 1.1520g Na2S.9H20,0.0948g Se powder on an electronic analytical balance added to the dispersion and stirred to obtain a uniform mixture; dispersed mixture was transferred into the 10mL reactor, while adding specifications 25mmX 75mm ITO transparent conductive glass substrate, and with ethanolamine volume to about 80% of the reactor volume.

[0055] 高温沉积:将反应釜加盖后拧紧密封,放入恒温箱中于180°C恒温沉积15h。 [0055] The high temperature deposition: The capped reaction vessel screwed tightly sealed, placed in a thermostatic oven at 180 ° C deposition temperature 15h.

[0056] 抽滤洗涤:随炉冷却至室温之后,取出玻璃基底,先后用去离子水和无水乙醇分别冲刷玻璃基底数次,直至洗液澄清并且无明显漂浮物。 [0056] suction filtration and washed: After furnace cooling to room temperature, the glass substrate removed, washed with deionized water and absolute ethanol, respectively, a glass substrate washed several times, until the washings were clear and no float.

[0057]干燥取样:将玻璃基底放入培养皿或者烧杯中,至于真空干燥箱中70°C干燥12h得CuIn(S,Se)2 薄膜。 [0057] The dried sample: the glass substrate into a beaker or culture dish, as in 70 ° C vacuum oven dried to give 12h CuIn (S, Se) 2 thin film.

[0058] 实施例4 [0058] Example 4

[0059]称量:分别在电子分析天平上称量0.8805g InCl3.4H20、0.5115g CuCl2.2H20,并将其转移至装有30mL乙醇胺的烧杯中,并用保鲜膜覆盖其上。 [0059] Weighing: 0.8805g InCl3.4H20,0.5115g CuCl2.2H20 were weighed on an electronic analytical balance and transferred to a beaker containing 30mL of ethanolamine, and covered with plastic wrap thereon.

[0060]分散:将烧杯放入超声分散机中,在功率为300W的超声下分散约30min得到分散液。 [0060] The dispersion: The beaker was placed in an ultrasonic dispersion machine, is dispersed at a power of 300W ultrasound to obtain a dispersion of about 30min.

[0061 ] 定容:再分别在电子分析天平上称量0.4320g Na2S.9H20、0.3318g Se粉加入分散液中,搅拌均匀得到混合液;将分散后混合液转移入10mL反应釜中,同时加入规格为25mmX 75mm的Mo玻璃基底,并用乙醇胺定容至反应釜容积的80%左右。 [0061] volume: then were weighed 0.4320g Na2S.9H20,0.3318g Se powder on an electronic analytical balance added to the dispersion and stirred to obtain a uniform mixture; dispersed mixture was transferred into the 10mL reactor, while adding Mo 25mmX 75mm specifications for the glass substrate, and with ethanolamine volume to about 80% of the reactor volume.

[0062] 高温沉积:将反应釜加盖后拧紧密封,放入恒温箱中于200°C恒温沉积15h。 [0062] The high temperature deposition: The capped reaction vessel screwed tightly sealed, placed in a thermostatic oven at 200 ° C deposition temperature 15h.

[0063] 抽滤洗涤:随炉冷却至室温之后,取出玻璃基底先后用去离子水和无水乙醇分别冲刷玻璃基底数次,直至洗液澄清并且无明显漂浮物。 [0063] suction filtration and washed: After furnace cooling to room temperature, remove the glass substrate washed with deionized water and absolute ethanol, respectively, a glass substrate washed several times, until the washings were clear and no float.

[0064]干燥取样:将玻璃基底放入培养皿或者烧杯中,至于真空干燥箱中70°C干燥12h得CuIn(S,Se)2 薄膜。 [0064] The dried sample: the glass substrate into a beaker or culture dish, as in 70 ° C vacuum oven dried to give 12h CuIn (S, Se) 2 thin film.

[0065] 实施例5 [0065] Example 5

[0066]性能测试: [0066] Performance Testing:

[0067]实施例3、4中的薄膜附着力测定采用[GB/T9286.1998](色漆和清漆漆膜划格试验)为测定标准,测定结果其附着力达到I〜O级,表明所制得的薄膜具有较高的附着力。 [0067] Examples 3 and 4 embodiments adhesion assay using membrane [GB / T9286.1998] (Paints and varnishes cut test) as a standard measurement, the measurement result reaches the adhesion I~O level, indicating that the obtained film has higher adhesion.

[0068] 对摩尔比3/(3+36)=0.2、0.4、0.6、0.8样品进行1^-¥丨8分析,比较了不同3元素掺杂量下CuIn(S,Se)2粉体的光吸收性能,结果如图4所示。 [0068] The molar ratio of 3 / (3 + 36) = 0.2,0.4,0.6,0.8 samples 1 ^ - ¥ 8 Shu analysis, comparing different amount of doping element 3 CuIn (S, Se) 2 powder light-absorbing properties, the results shown in Figure 4. 由图分析可知,CuIn(S,Se)2粉体在在紫外-可见光区的光吸收能力均较强。 FIG analysis shows, CuIn (S, Se) 2 powder in the UV - are strong light absorptive visible light region. 但是随着S掺杂量的增加而减小,即在同等光波长下,CuIn(S,Se)2粉体的光吸收边出现“蓝移”现象。 However, with the increase in doping amount S is reduced, i.e. light in the same wavelength, CuIn (S, Se) 2 powder light absorption edge of a "blue shift" phenomenon. 通过光吸收性能公式估测样品的禁带宽度分别为:1.27eV、1.32eV、1.36eV和1.40eV,表明通过控制S元素的掺杂量可以实现对样品带隙的有效调控。 Sample estimated by optical absorption band gap formula are: 1.27eV, 1.32eV, 1.36eV ​​and 1.40eV, indicate that effective control can be achieved with the sample gap amount S by controlling the doping element.

[0069]以实施例4中的空白玻璃基底作为对照,采用UV-2100型紫外-可见分光光度计测量样品的光吸收曲线,实验结果如图5所示,从图中可以看出,实施例4所得到的薄膜样品在紫外-可见光区域也具有较好的光吸收能力,特别是在可见光区域的光吸收度较高,表明其具有良好的可见光响应活性,可用作薄膜太阳能电池的吸收层材料。 [0069] In a blank glass substrate in Example 4 As a control, using UV-2100 UV - visible spectrophotometer measuring the light absorption curve of the sample, the experimental results shown in Figure, it can be seen from FIG. 5, Example the film sample 4 obtained in the UV - visible light region also has good absorption capacity, especially high light absorbance in the visible region, which showed good activity in response to visible light, it can be used as the absorbent layer of thin film solar cell material.

Claims (6)

  1. 1.一种用于薄膜太阳能电池的铜铟硫砸薄膜的制备方法,其特征在于,先将氯化铜和氯化铟分散于有机溶剂中,超声分散后得到分散液;在所得分散液中加入硫化钠和砸粉后,搅拌均匀,得到混合液,加入的硫化钠和砸粉中S和Se的摩尔关系满足S/ (S+Se) = 0.1〜0.9;将所述混合液移至反应釜中,再加入玻璃基底,定容、密封,在160〜220°C下液相沉积,将沉积得到的玻璃基底用去离子水和无水乙醇洗涤,真空干燥,得到CuIn(S,Se)2薄膜。 The method of preparing a copper indium film A thin film solar cell of sulfur for smashing, characterized in that the first copper chloride and indium chloride dispersed in an organic solvent, after ultrasonic dispersion to obtain a dispersion; in the resultant dispersion after addition of sodium sulfide powder and crushing the mixture was stirred uniformly to obtain a mixture, the added powder sodium sulfide and hit S and Se molar relationship satisfying S / (S + Se) = 0.1~0.9; the reaction mixture was moved vessel, then the glass substrate was added, volume, sealed, liquid deposited at 160~220 ° C, the glass substrate was washed with deionized water and the resulting deposition of anhydrous ethanol and dried in vacuo to give CuIn (S, Se) 2 film.
  2. 2.如权利要求1所述的制备方法,其特征在于,所述的液相沉积的时间为12〜15h。 The production method as claimed in claim 1, wherein said liquid deposition time was 12~15h.
  3. 3.如权利要求1所述的制备方法,其特征在于,所述的有机溶剂为无水乙醇胺、无水乙二胺中一种或两种。 The production method as claimed in claim 1, wherein said organic solvent is anhydrous ethanol amine, one or two of anhydrous ethylenediamine.
  4. 4.如权利要求1所述的制备方法,其特征在于,所述的超声分散是在功率为200〜300W的超声下分散20〜60min。 4. The method as recited in claim 1, wherein said ultrasonic dispersion is dispersed in 20~60min 200~300W ultrasound power.
  5. 5.如权利要求1所述的制备方法,其特征在于,所述的真空干燥是在60〜80°C下,真空干燥8〜12h。 5. The method as recited in claim 1, wherein said vacuum drying is at 60~80 ° C, and dried in vacuo 8~12h.
  6. 6.如权利要求1〜5任一项所述的制备方法,其特征在于,所述的玻璃基底为光学玻璃。 The method of preparation according to any one of claim 1 ~ 5, wherein said glass substrate is an optical glass.
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CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof
CN102249549A (en) * 2011-04-01 2011-11-23 中南大学 Copper-indium-selenium photovoltaic film, powder and coating material for solar batteries and preparation method thereof
CN102249199A (en) * 2011-05-06 2011-11-23 桂林理工大学 Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder

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CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof
CN102249549A (en) * 2011-04-01 2011-11-23 中南大学 Copper-indium-selenium photovoltaic film, powder and coating material for solar batteries and preparation method thereof
CN102249199A (en) * 2011-05-06 2011-11-23 桂林理工大学 Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder

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