WO2021227362A1 - 铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 - Google Patents

铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 Download PDF

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WO2021227362A1
WO2021227362A1 PCT/CN2020/121966 CN2020121966W WO2021227362A1 WO 2021227362 A1 WO2021227362 A1 WO 2021227362A1 CN 2020121966 W CN2020121966 W CN 2020121966W WO 2021227362 A1 WO2021227362 A1 WO 2021227362A1
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copper
tin
zinc
solution
thiourea
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PCT/CN2020/121966
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English (en)
French (fr)
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辛颢
张一凡
龚元才
牛传友
邱瑞婵
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南京邮电大学
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Priority to EP20935195.6A priority Critical patent/EP4152416A4/en
Publication of WO2021227362A1 publication Critical patent/WO2021227362A1/zh
Priority to US17/986,902 priority patent/US20230070055A1/en

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    • C—CHEMISTRY; METALLURGY
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    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3628—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a sulfide
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    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • 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

Definitions

  • the invention belongs to the technical field of new energy photovoltaic power generation, and specifically relates to a precursor solution of a copper-zinc-tin-sulfur thin-film solar cell and a preparation method and application thereof, in particular to the preparation and application of photovoltaic devices.
  • Copper zinc tin sulphur (CZTS) material and copper indium gallium selenium (CIGS) material have similar crystal structure and optical band gap.
  • the absorption coefficient in the visible light range is> 10 4 /cm, and the band gap is adjustable in the range of 1.0 to 1.5 eV, which is compatible with solar energy.
  • the battery material matches the optimal optical band gap interval, and has a high theoretical conversion efficiency (32.3%).
  • the preparation methods of copper-zinc-tin-sulfur film materials are mainly divided into two categories: vacuum method and solution method.
  • the traditional vacuum preparation method is based on a high vacuum environment, and its material preparation process has high energy consumption and low material utilization.
  • the solution method is based on chemical solutions, does not require a vacuum environment, has low energy consumption, can be used for large-area film formation, and has advantages such as improved material utilization and low-temperature processing.
  • the present invention discloses a simple, novel, stable, and environmentally-friendly precursor solution preparation scheme, which has been successfully applied to copper-zinc-tin-sulfur film selenium film materials and copper-zinc-tin-sulfur
  • the prepared copper-zinc-tin-sulfur-selenium material has high crystalline quality, good morphology, no miscellaneous phases, and its photovoltaic device energy conversion efficiency exceeds 10%, indicating the remarkable advancement of the invention.
  • the present invention provides a precursor solution of a copper zinc tin sulfur (CZTS) thin film solar cell, as well as a cell preparation method and application thereof, to prepare a high-efficiency copper zinc tin sulfur solar cell Purpose, by using the copper complex formed by copper salt and thiourea as the precursor of copper, and the tin complex formed by tin salt and dimethyl sulfoxide or N,N-dimethylformamide as the precursor of tin, it is simple Zinc salt is used as a precursor of zinc, a stable precursor solution is prepared to prepare high-quality, impurity-free copper-zinc-tin-sulfur light-absorbing material, and a copper-zinc-tin-sulfur thin-film solar cell with high photoelectric conversion efficiency is prepared.
  • CZTS copper zinc tin sulfur
  • the copper complex is a complex formed by a copper salt and thiourea or a derivative of thiourea, including: a complex formed by a halogen copper salt and thiourea, Cu(Tu) 3 X, wherein X includes F,
  • the halogen elements such as Cl, Br and I
  • the copper complexes formed include: Cu(Tu) 3 Cl, [Cu 2 (Tu) 6 ]Cl 2 ⁇ 2H 2 O, Cu(Tu) 3 Br;
  • the tin complex is selected from Sn(X) y Cl 4 , Sn(X) y F 4 , Sn(X) y Br 4 , Sn(X) y I 4 , Sn(X) y (CH 3 COO) one or more of 4
  • X is selected from one of DMSO, DMF, ethanol, and N-methylpyrrolidone
  • y is a natural number greater than zero.
  • the zinc salt is a compound of divalent zinc, including but not limited to halogen zinc salt, zinc acetate, zinc nitrate, and zinc sulfate.
  • the amount of thiourea substance is (0-1):1.
  • the amount of copper element is (1.5 ⁇ 2.5):1;
  • the amount of zinc element is (0.9 ⁇ 1.5):1;
  • the amount of sulfur element the sum of the amount of copper, tin and zinc element is (1.0 ⁇ 6.0):1.
  • the concentration of copper element in the solution is 0.05mol/L ⁇ 5mol/L;
  • the concentration of tin element in the solution is 0.05mol/L ⁇ 5mol/L;
  • the concentration of zinc element in the solution is 0.05mol/L ⁇ 5mol/L;
  • the concentration of sulfur in the solution is 0.15 mol/L to 5 mol/L.
  • the present invention also discloses a method for preparing the precursor solution of the above-mentioned copper-zinc-tin-sulfur solar cell.
  • the specific method for preparing the precursor solution is a step-by-step preparation method: using DMSO or DMF as a solvent, the copper complex and thiourea are dissolved in Solution 1 is prepared in the solvent, in which the amount of thiourea substance: the amount of copper element is not more than 1; the tin complex and zinc salt are dissolved in the solvent to prepare solution 2; the solution 1 and solution 2 are mixed to obtain a clear and transparent precursor Body solution.
  • Synthesis of copper complex dissolve thiourea in deionized water, add copper salt to the solution after thiourea is completely dissolved, the ratio of the added thiourea to copper salt is 3:1, and the temperature of the solution during the reaction The temperature is 70 degrees Celsius; after dissolution, the solution is filtered, left to stand, and slowly cooled, the copper complex crystals of the target product are precipitated from the solution, and the above crystal products are taken out and dried;
  • Synthesize tin complex take the tetravalent tin salt in a round bottom flask, seal the mouth of the bottle, and pour the organic compound solvent DMF or DMSO into the bottle.
  • the ratio of the organic compound to the tin salt substance in the solvent is 2-20; tin
  • the salt reacts with DMF or DMSO solvent to generate a large amount of white precipitate.
  • the precipitate is washed with ethanol and dried to obtain the corresponding target tin complex.
  • the above-mentioned method for preparing a precursor solution of a high-efficiency copper-zinc-tin-sulfur solar cell and its application to the preparation of a copper-zinc-tin-sulfur solar cell includes the following steps:
  • step 2 The copper-zinc-tin-sulfur precursor film generated in step 2 is heated and reacted in an atmosphere of Se to partially or completely replace the S atoms with Se atoms to generate a copper-zinc-tin-sulfur thin film material;
  • a grid electrode of 50 nm of metal Ni and 1 ⁇ m of Al is deposited on the surface of the sample obtained in step 5 by a thermal evaporation method.
  • reaction conditions of spin coating and annealing in step 4 are: spin coating rotation speed is 500-8000 rpm, time is 10-600 s, annealing temperature is 200-500°C, heating time is 20-120 s, and spin-coating annealing is repeated 3 to 15 times.
  • step 5 the specific steps of the selenization reaction in step 5 are as follows:
  • the target temperature is 500°C ⁇ 600°C
  • the heating rate is 0.2°C ⁇ 10°C/s
  • the annealing is at the target temperature for 5 ⁇ 30 minutes.
  • the method for preparing a precursor solution of a copper-zinc-tin-sulfur thin-film solar cell has the following advantages:
  • the present invention discloses two types of simple synthesis methods of metal complexes and used to prepare stable precursor solutions.
  • the use of metal complexes maintains the initial valence state of the metal precursor and avoids monovalent copper ions and tetravalent tin
  • the ion undergoes oxidation-reduction reaction, and the obtained precursor solution has good quality, good stability and good repeatability.
  • the precursor solution prepared in the present invention can prepare high-quality, impurity-free copper-zinc-tin-sulfur light-absorbing materials, and the prepared copper-zinc-tin-sulfur thin-film solar cell has high photoelectric conversion efficiency.
  • FIG. 1 The physical diagram of the copper complex Cu(Tu) 3 Cl formed by the formation of cuprous chloride and thiourea in the examples.
  • FIG. 1 The physical diagram of the tin complex Sn(DMF) 2 Cl 4 formed by tin tetrachloride and N,N-dimethylformamide in Example 3.
  • Figure 9 The Raman spectrum of the precursor film in the first embodiment.
  • FIG. 13 Scanning electron micrograph (cross-section of the film) of the absorber film in the first embodiment.
  • FIG. 14 Scanning electron micrograph (cross-section of the film) of the absorber film in the third embodiment.
  • FIG. 1 Scanning electron micrograph of the absorber film in the first embodiment (film surface).
  • Figure 17 The voltage-current characteristic curve of the copper-zinc-tin-sulfur-selenium solar cell device in the first embodiment under the AM1.5G standard sunlight intensity.
  • Figure 18 The voltage-current characteristic curve of the copper-zinc-tin-sulfur-selenium solar cell device in the third embodiment under the AM1.5G standard sunlight intensity.
  • the invention discloses a preparation method of a precursor solution of a high-efficiency copper-zinc-tin-sulfur solar cell and preparation and application of photovoltaic devices.
  • the present invention discloses two types of simple metal complexes for preparing precursor solutions with excellent stability.
  • the precursor solutions prepared by using metal complexes as precursor compounds have good stability and reproducibility, and can be used to prepare high crystal quality and thin film shapes.
  • the copper-zinc-tin-sulfur thin-film light-absorbing material with good appearance and no impurity phase, the copper-zinc-tin-sulfur thin-film solar cell prepared by this has high photoelectric conversion efficiency.
  • the use of metal complexes simplifies the preparation process of the precursor solution, improves the quality of the precursor solution, and improves the energy conversion efficiency of photovoltaic devices, which has great potential for industrial application.
  • Step 1 Preparation of copper complex.
  • Step 2 Preparation of tin complex.
  • Step 3 Preparation of precursor solution.
  • Step 4 Preparation of copper-zinc-tin-sulfur (copper-zinc-tin-sulfur) precursor film.
  • the molybdenum-plated glass was ultrasonically cleaned in acetone and isopropanol for 10 minutes, and then dried.
  • the precursor solution prepared in step 3 was spin-coated in a glove box, and the spin-coating parameters were spin-coating speed 1500 rpm and spin-coating time 60 s. After the spin coating is finished, put the sample on a hot stage at 420°C for 2 minutes to anneal. Repeat the above spin-coating-heating process 7 times to obtain a copper-zinc-tin-sulfur precursor film.
  • Step 5 Preparation of copper zinc tin sulfur selenium (copper zinc tin sulfur Se) film.
  • step 4 Place the two precursor film samples (2.45cm ⁇ 2.45cm) prepared in step 4 in a graphite box, weigh about 0.35g of Se particles into the graphite box symmetrically, close the valve tightly, and evacuate to make the vacuum degree in the tube reach After 3 ⁇ 10 -2 Torr, pour argon gas into the tube, repeat the above operation 3 times to purge the air in the tube to ensure that the selenization reaction is carried out in an anhydrous and oxygen-free environment. Start the heating program of the tube furnace, the target temperature is 550°C, the heating rate is 2°C/s, and the annealing is performed at 550°C for 20 minutes. After annealing, the sample is naturally cooled to room temperature.
  • Step 6 Preparation of CdS buffer layer.
  • Step 1 Set the temperature of the water bath to 65°C, measure 22mL of 0.75mol/L thiourea solution, 22mL of 0.015mol/L cadmium sulfate solution, and 28mL of ammonia with a graduated cylinder.
  • Step 2 Pour the amount of ammonia and cadmium sulfate solution into 150mL ultrapure water and mix, pour the mixed solution into a water jacketed beaker, and then put the sample soaked in ultrapure water into the water jacketed beaker mixed solution . Fill 65°C circulating water into the interlayer of the water-jacketed beaker to heat and start timing.
  • Step 3 Pour the pre-measured thiourea solution into the reaction solution after one minute. As the reaction progressed, the solution changed from clear to light yellow, and finally turned into a yellow translucent suspension.
  • Step 4 Take out the sample after the solution reacts for eight minutes, rinse the surface of the sample with ultrapure water to remove the CdS particles adsorbed on the surface, and then blow the sample dry with a nitrogen gun.
  • Step 7 Preparation of the window layer (ZnO/ITO).
  • Intrinsic zinc oxide (i-ZnO) and indium tin oxide (ITO) were deposited on the above samples by magnetron sputtering as window layer materials.
  • Magnetron sputtering instrument sputtering i-ZnO, sputtering power 80W, pure argon atmosphere, pressure of 0.5Pa, and film thickness of 50nm.
  • the sputtering power of sputtering ITO is 60W
  • the sputtering pressure of pure argon atmosphere is 0.5Pa
  • the film thickness is 200nm.
  • Step 8 Preparation of the electrode (Ni/Al).
  • the cathode of the battery is composed of metal Ni and Al and is prepared by thermal evaporation method.
  • the thickness of Ni and Al are 50nm and 500nm, respectively.
  • the copper-zinc-tin-sulfur precursor film layer and the absorption film layer prepared according to the above process are free of impurity phases, and the absorption layer material has high crystallinity and good morphology.
  • the energy conversion efficiency of the prepared copper-zinc-tin-sulfur solar cell is 10.9%.
  • Step 1 Preparation of copper complex.
  • the operation method of this step is the same as that of implementation example 1.
  • Step 2 Weigh 12.53 grams of tin tetrachloride into a round bottom flask, seal the mouth of the bottle, and take 50ml of DMF and inject it into the bottle through a syringe. After the two substances are in contact, they react violently and produce a large amount of white precipitate. After the completion of the reaction, the reaction solution was filtered to obtain a white precipitate, which was washed several times with ethanol and dried to obtain the target product Sn(DMF) 2 Cl 4 .
  • Step 3 Preparation of precursor solution. Measure 8mL DMSO into the reagent bottle, weigh 2.0g (6.12mmol) of the copper complex prepared in step 1, 1.626g (4mmol) of the tin complex Sn(DMF) 2 Cl 4 prepared in step 2, 0.734g ( 4mmol) zinc acetate and 0.2g thiourea were added to the reagent bottle and stirred at room temperature until completely dissolved.
  • Step 4 to Step 8 The operation method is the same as the first implementation example.
  • Step 1 Preparation of copper complex.
  • the operation method of this step is the same as that of implementation example 1.
  • Step 2 Weigh 12.53 grams of tin tetrachloride into a round bottom flask, seal the mouth of the bottle, and take 50ml of DMSO and inject it into the bottle through a syringe. After the two substances are in contact, they react violently and produce a large amount of white precipitate. After the reaction is complete. After the completion of the reaction, the reaction solution was filtered to obtain a white precipitate, washed with ethanol several times, and dried to obtain the target product Sn(DMSO) 4 Cl 4 .
  • Step 3 Preparation of precursor solution. Weigh 8 mL of DMF into the reagent bottle, weigh out 2.0 g (6.12 mmol) of the copper complex Cu(Tu) 3 Cl prepared in step 1, and 1.667 g (4 mmol) of the tin complex Sn(DMSO) 4 Cl prepared in step 2 4. 0.734g (4mmol) zinc acetate and 0.2g thiourea were added to the reagent bottle and stirred at room temperature until completely dissolved.
  • Step 4 to Step 8 The operation method is the same as the first implementation example.
  • Step 1 Preparation of copper complex.
  • the operation method of this step is the same as that of implementation example 1.
  • Step 2 Weigh 12.53 grams of tin tetrachloride into a round bottom flask, seal the mouth of the bottle, and take 50ml of DMF and inject it into the bottle through a syringe. After the two substances are in contact, they react violently and produce a large amount of white precipitate. After the completion of the reaction, the reaction solution was filtered to obtain a white precipitate, washed with ethanol for several times, and dried to obtain the target tin complex Sn(DMF) 2 Cl 4 .
  • Step 3 Preparation of precursor solution. Measure 8mL DMF into the reagent bottle, weigh 2.0g (6.12mmol) of the copper complex prepared in step 1, 1.626g (4mmol) of the tin complex Sn(DMF) 2 Cl 4 prepared in step 2, 0.734g (4mmol) ) Zinc acetate and 0.2 g of thiourea were added to the reagent bottle and stirred at room temperature until completely dissolved.
  • Step 4 to Step 8 The operation method is the same as the first implementation example.
  • the embodiment of the present invention provides four new preparation methods for preparing precursor solutions of high-efficiency CZTS solar cells, that is, by using metal complexes as precursor compounds to prepare precursor solutions, the prepared crystal quality is high, the film morphology is good, and there is no
  • the impurity phase copper-zinc-tin-sulfur thin film light-absorbing material can prepare high-efficiency copper-zinc-tin-sulfur solar cells.
  • Figure 1 and Figure 2 are the actual photos of the copper complex and the tin complex.
  • the chemical components of the copper complex and tin complex are analyzed by an elemental analyzer as Cu(Tu) 3 Cl and Sn(DMF) 2 Cl.
  • Figures 3 and 4 are photos of the precursor solutions prepared based on the above two metal complexes in DMSO and DMF solvents. It can be observed that the two solutions are clear and transparent without precipitation and impurities, and the stability is good, indicating The quality of the solution is high.
  • Figures 5 and 6 show the X-ray diffraction patterns of the precursor films formed by spin coating and annealing of the two precursor solutions.
  • Figures 9 and 10 show the Raman spectra of the precursor films. The two precursor films have obvious Raman vibration peaks at the Raman shift of 337 cm -1 , corresponding to the CZTS phase.
  • Figure 11 and Figure 12 are the Raman spectra of the Cu-Zn-Sn-S-S-absorbing film. It can be seen from the figure that the two precursor films have obvious Raman shifts at 172, 193, and 231 cm -1 The vibration peak corresponds to the copper zinc tin selenium phase (CZTSe), and the Raman vibration peak without other impurity phases can be observed. This indicates that the prepared absorber film is a high-quality copper-zinc-tin-sulfur-selenium film. Combining the scanning electron micrographs of the absorption film with high crystallinity, flatness, compactness, and impurity-free phases observed in Figs. 13, 14, 15 and 16, further shows that the absorption layer film prepared in the example is of high quality.
  • the two sets of light-absorbing film layers are prepared into solar cell devices and tested for photovoltaic performance. Their voltage-current characteristic curves are shown in Figures 17 and 18. The photoelectric conversion efficiency of the two devices exceeds 10%, reaching the international advanced level. .
  • the technical scheme of the present invention prepares a stable, clear and transparent high-quality precursor solution, and applies it to the preparation of copper, zinc, tin, sulfur, selenium film materials and photovoltaic devices, and finally, the crystal quality is high, the morphology is good, and there is no
  • the miscellaneous copper-zinc-tin-sulfur-selenium film materials and photovoltaic devices with an energy conversion efficiency of more than 10% indicate the remarkable advancement of the invention.

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Abstract

本发明公开了一种铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用，本发明公开了两类可配制优质前驱体溶液的简单金属配合物，通过使用金属配合物作为前驱体化合物，配制的前驱体溶液稳定性好，可用来制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，以此制备的铜锌锡硫薄膜太阳能电池光电转化效率高。金属配合物的使用，简化了前驱体溶液配制流程，提升了前驱体溶液质量，提高了光伏器件能量转换效率，具有极大的工业应用潜力。

Description

铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用 技术领域
本发明属于新能源光伏发电技术领域，具体涉及一种铜锌锡硫薄膜太阳能电池的前驱体溶液及其制备方法与应用，具体是用于光伏器件的制备与应用。
背景技术
能源短缺问题是制约人类未来发展的关键问题，可再生能源的开发和利用是解决该问题的优质方案，光伏发电技术是可再生能源中最具前景的发展方向。过去几十年，以单晶硅和多晶硅为代表的硅基太阳能电池和以碲化镉(CdTe)和铜铟镓硒(CIGS)为代表的多元化合物半导体薄膜太阳能电池在能量效率方面取得了长足的进步，已成功实现商业化生产。目前单晶硅电池实验室获得的最高光电转换效率达到26.7％，CIGS和CdTe薄膜太阳能电池在实验室获得的最高光电转换效率也分别达到23.35％和22.1％。但由于硅半导体的低吸光系数，低缺陷耐受性差，Cd元素潜在的环境毒害性，In、Ga、Te元素的地壳资源稀缺性等因素，导致这些光伏器件的制作成本居高不下，难以与传统能源进行市场竞争。铜锌锡硫(CZTS)材料与铜铟镓硒(CIGS)材料具有相似的晶体结构和光学带隙，可见光范围吸光系数＞10 4/cm，带隙在1.0～1.5eV范围可调，与太阳能电池材料的最佳光学带隙区间相匹配，具有较高的理论转化效率(32.3％)，同时它的组成元素地球储藏极其丰富，价格低廉，安全无毒，是有望取代铜铟镓硒的新型低成本光伏材料。铜锌锡硫膜层材料的制备方法主要分为真空法和溶液法两大类。传统的真空制备法以高真空环境为基础，其材料制备过程能耗高，材料利用率较低。溶液法以化学溶液为基础，无需真空环境，其能耗较低，可用于大面积成膜，还具备提高材料利用率和低温加工等优点。
分子前驱体溶液法因工艺简单，制备的电池转换效率较高，在近些年颇受研究者关注。2013年IBM公司报道了基于肼溶剂的前驱体溶液法制备得到能量转化效率为12.6％的铜锌锡硫硒太阳能电池。但是由于肼的易爆性和高毒害性限制了该方法的应用。美国华盛顿大学Hillhouse课题组提出了低危害性的基于二甲基亚砜溶剂的前驱体溶液方案，但由于溶液中阳离子氧化还原反应的存在，限制了所制备的太阳能电池效率的提高。鉴于此，通过对溶液化学的研究，本发明公开一种简单、新颖、稳定、绿色环保的前驱体溶液配制方案，该方案被成功应用于铜锌锡硫膜硒膜层材料和铜锌锡硫硒太阳能电池的制备，制备得到的铜锌锡硫硒材料结晶质量高，形貌好，无杂相，其光伏器件能量转化效率超过10％，表明该发明显著的先进性。
发明内容
发明目的：为了克服现有技术中存在的不足，本发明提供一种铜锌锡硫(CZTS)薄膜太阳能电池的前驱体溶液及其电池制备方法与应用，以制备高效铜锌锡硫太阳能电池为目的，通过使用铜盐与硫脲形成的铜配合物作为铜的前驱体，锡盐与二甲基亚砜或N,N-二甲基甲酰胺生成的锡配合物作为锡的前驱体，简单锌盐作为锌的前驱体，配制稳定的前驱体溶液，制备高质量、无杂质相的铜锌锡硫吸光材料，制备高光电转化效率的铜锌锡硫薄膜太阳能电池。
技术方案：为实现上述目的，本发明采用的技术方案为：
一种铜锌锡硫太阳能电池的前驱体溶液，以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质配制；所述前驱体化合物由金属配合物、金属化合物和硫脲组成，其中，所述金属配合物为铜盐与硫脲或硫脲衍生物形成的铜配合物、锡盐与DMF或DMSO形成的锡配合物，金属化合物为二价锌盐；将以上前驱体化合物溶解在DMSO或DMF溶剂中得到稳定、澄清透明的前驱体溶液。
进一步的，所述铜配合物为铜盐与硫脲或硫脲的衍生物形成的配合物，包括：卤素铜盐与硫脲形成的配合物Cu(Tu) 3X，其中X为包括F、Cl、Br、I在内的卤族元素，所形成的铜配合物包括：Cu(Tu) 3Cl，[Cu 2(Tu) 6]Cl 2·2H 2O,Cu(Tu) 3Br；还包括卤素铜盐与硫脲衍生物形成的配合物：Cu(DMTu) 3Br，Cu(TMTu) 3Cl，[Cu(ETu) 2Br] 2，其中DMTu为N,N-二甲基硫脲，TMTU为四甲基硫脲，ETu为乙撑硫脲；还包括硝酸铜盐与硫脲形成的配合物Cu 4(Tu) 10(NO 3)·Tu·3H 2O。
进一步的，所述锡配合物选自Sn(X) yCl 4，Sn(X) yF 4,Sn(X) yBr 4,Sn(X) yI 4,Sn(X) y(CH 3COO) 4中的一种或多种，X选自DMSO、DMF、乙醇、N-甲基吡咯烷酮中的一种，y为大于零的自然数。
进一步的，所述锌盐为二价锌的化合物，包括但不限于卤素锌盐、乙酸锌、硝酸锌、硫酸锌。
进一步的，所述前驱体溶液中，硫脲物质的量：铜元素的物质的量为(0～1)：1。
进一步的，所述前驱体化合物中：
铜元素的物质的量：锡元素的物质的量为(1.5～2.5)：1；
锌元素物质的量：锡元素的物质的量为(0.9～1.5)：1；
硫元素物质的量：铜、锡与锌元素物质的量之和为(1.0～6.0)：1。
进一步的，所述前驱体溶液中：
铜元素在溶液中浓度为0.05mol/L～5mol/L；
锡元素在溶液中浓度为0.05mol/L～5mol/L；
锌元素在溶液中浓度为0.05mol/L～5mol/L；
硫元素在溶液中浓度为0.15mol/L～5mol/L。
本发明还公开了上述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，制备前驱体溶液的具体方法为分步制备法：以DMSO或DMF为溶剂，将铜配合物和硫脲溶解在溶剂中制备溶液一，其中硫脲物质的量：铜元素的物质的量不大于1；将锡配合物和锌盐溶解在溶剂中制备溶液二；将溶液一和溶液二混合得到澄清透明的前驱体溶液。
进一步的，铜配合物、锡配合物的制备方法为：
合成铜配合物：将硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度；溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出，取出上述晶体产物并烘干；
合成锡配合物：取四价锡盐于圆底烧瓶中，密封瓶口，取有机化合物溶剂DMF或DMSO注入瓶中，其中溶剂中有机化合物与锡盐物质的量之比为2～20；锡盐与DMF或DMSO溶剂反应生成大量白色沉淀，用乙醇将沉淀清洗干净，烘干即得相应目标产物锡配合物。
上述的一种高效铜锌锡硫太阳能电池的前驱体溶液制备方法及将其应用于铜锌锡硫太阳能电池的制备，包括以下步骤：
(1)合成铜配合物：将一定量硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度。两种物质基本溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出。过滤得到上述晶体产物，烘干。
(2)合成锡配合物：取一定量四价锡盐于圆底烧瓶中并密封瓶口，取过量有机化合物DMF或DMSO注入瓶中，反应生成大量白色沉淀，过滤，使用乙醇将沉淀清洗干净，烘干即得目标产物锡配合物。
(3)制备前驱体溶液：以DMSO或DMF为溶剂，将铜配合物、锡配合物、二价锌化合物和硫脲溶解在溶剂中，得到澄清透明的前驱体溶液；
(4)将步骤1中获得的前驱体溶液旋涂在钼玻璃上，加热退火生成铜锌锡硫前驱体薄膜；
(5)将步骤2中生成的铜锌锡硫前驱体薄膜在Se的气氛中加热反应，以Se原子部分或者全部取代S原子生成铜锌锡硫薄膜材料；
(6)将硒化反应后的铜锌锡硫Se膜取出，用超纯水浸泡后置于含有氨水、硫酸镉和硫脲溶液的水夹套烧杯中，在加热情况下进行反应，在铜锌锡硫Se膜表面沉积一层CdS；
(7)通过磁控溅射技术在步骤4的样品表面依次溅射50nm本征氧化锌(i-ZnO)以及250nm铟锡氧化物(ITO)作为窗口层；
(8)通过热蒸镀方法在步骤5获得的样品表面依次蒸镀50nm金属Ni和1μm Al的栅形 电极。
进一步的，步骤4中旋涂与退火的反应条件为：旋涂转速为500～8000rpm，时间为10～600s，退火温度为200～500℃，加热时间为20～120s，重复旋涂退火3～15次。
进一步的，步骤5硒化反应的具体步骤如下：
(5-1)将铜锌锡硫薄膜与0.2～0.5g的硒粒置于石墨盒中，然后将石墨盒水平缓慢放入石英管中，石英管两端法兰连有气体管路，气体管路上连有压力表与气体阀门；
(5-2)用机械泵将石英管中的气体抽至3×10 -2Torr以下，然后充入氩气至管中气压为常压；
(5-3)启动管式炉加热程序，目标温度为500℃～600℃，升温速率为0.2℃～10℃/s，在目标温度下退火5～30分钟。
(5-4)退火程序终止后，自然冷却至室温。
有益效果：本发明提供的一种铜锌锡硫薄膜太阳能电池的前驱体溶液制备方法，与现有技术相比，具有以下优势：
1.本发明公开了两类简单的金属配合物的合成方法并用来配制稳定的前驱体溶液，金属配合物的使用保持了金属前驱体的初始价态，避免了一价铜离子与四价锡离子发生氧化还原反应，得到的前驱体溶液质量优，稳定性好，重复性好。
2.本发明制备的前驱体溶液可制备高质量、无杂质相的铜锌锡硫吸光材料，制备的铜锌锡硫薄膜太阳能电池的光电转化效率高。
3.金属配合物的使用，简化了溶液配制流程，大幅缩短溶液配制时间，利于工业化生产。
附图说明
图1、实施例中氯化亚铜与硫脲的生成的铜配合物Cu(Tu) 3Cl的实物图。
图2、实施例三中四氯化锡与N,N-二甲基甲酰胺生成的锡配合物Sn(DMF) 2Cl 4的实物图。
图3、实施例一中的DMSO前驱体溶液实物图。
图4、实施例三中的DMF前驱体溶液实物图。
图5、实施例一中前驱体薄膜的X射线衍射图谱。
图6、实施例三中的前驱体薄膜的X射线衍射图谱。
图7、实施例一中的吸收层薄膜的X射线衍射图谱。
图8、实施例三中的吸收层薄膜的X射线衍射图谱。
图9、实施例一中的前驱体薄膜的拉曼光谱。
图10、实施例三中的前驱体薄膜的拉曼光谱。
图11、实施例一中的吸收层薄膜的拉曼光谱。
图12、实施例三中的吸收层薄膜的拉曼光谱。
图13、实施例一中的吸收层薄膜的扫描电镜图(膜层横截面)。
图14、实施例三中的吸收层薄膜的扫描电镜图(膜层横截面)。
图15、实施例一中的吸收层薄膜的扫描电镜图(膜层表面)。
图16、实施例三中的吸收层薄膜的扫描电镜图(膜层表面)。
图17、实施例一中的铜锌锡硫硒太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。
图18、实施例三中铜锌锡硫硒太阳能电池器件在AM1.5G标准太阳光强下的电压-电流特性曲线。
具体实施方式
本发明公开了一种高效铜锌锡硫太阳能电池的前驱体溶液的制备方法及其光伏器件的制备与应用。本发明公开了两类配制稳定性能优异的前驱体溶液的简单金属配合物，通过使用金属配合物作为前驱体化合物配制的前驱体溶液稳定性和重复性好，可用来制备结晶质量高，薄膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，以此制备的铜锌锡硫薄膜太阳能电池光电转化效率高。金属配合物的使用，简化了前驱体溶液配制流程，提升了前驱体溶液质量，提高了光伏器件能量转换效率，具有极大的工业应用潜力。
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实例。
根据下述实施例，可以更好的理解本发明。然而，本领域的技术人员容易理解，实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
实施示例一：
步骤一：铜配合物的制备。
称取45.67g(0.6mol)硫脲溶解于100ml去离子水中，加热搅拌保持溶液温度为70℃，待硫脲完全溶解，称取19.8g(0.2mol)氯化亚铜加入其中，反应30分钟后，大部分氯化亚铜溶解，将溶液热过滤，将滤液静置，自然冷却。一段时间后滤液中析出无色透明晶体即为目标产物铜配合物Cu(Tu) 3Cl，过滤，烘干。
步骤二：锡配合物的制备。
称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMSO通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物Sn(DMSO) 4Cl 4。
步骤三：前驱体溶液的制备。
量取8mLDMSO至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.667g(4mmol)步骤二中制备的锡配合物Sn(DMSO) 4Cl 4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四：铜锌锡硫(铜锌锡硫)前驱体薄膜的制备。
将镀钼玻璃在丙酮和异丙醇中各超声清洗10分钟后吹干。在手套箱中对步骤三制备的前驱体溶液进行旋涂，旋涂参数为旋涂速度1500转/分，旋涂时间60s。旋涂结束后，将样品放到420℃的热台上退火2min。重复以上旋涂-加热过程7次，得到铜锌锡硫前驱体薄膜。
步骤五：铜锌锡硫硒(铜锌锡硫Se)薄膜的制备。
将步骤四制备的两片前驱体薄膜样品(2.45cm×2.45cm)置于石墨盒中，称量约0.35g的Se粒对称放入石墨盒中，将阀门关紧，抽真空使管内真空度达到3×10 -2Torr后往管内通入氩气，重复以上操作3次以排净管内的空气，确保硒化反应在无水无氧环境下进行。启动管式炉加热程序，目标温度为550℃，升温速率为2℃/s，在550℃下退火20分钟。退火结束后样品自然冷却至室温。
步骤六：缓冲层CdS的制备。
硒化反应结束后，将石墨盒中的样品取出置于超纯水中浸泡6min，然后通过化学浴沉积法(CBD)沉积CdS缓冲层。第一步：设置水浴温度为65℃，用量筒分别量取22mL浓度为0.75mol/L的硫脲溶液，22mL浓度为0.015mol/L的硫酸镉溶液以及28mL的氨水。第二步：将量好的氨水和硫酸镉溶液倒入150mL超纯水中混合，将混合溶液倒入水夹套烧杯中，随后将超纯水浸泡的样品放入水夹套烧杯混合溶液中。将65℃的循环水充入水夹套烧杯的夹层加热并开始计时。第三步：一分钟后将预先量取好的硫脲溶液倒入反应溶液中。随着反应的进行，溶液由澄清变为淡黄，最终变为黄色的半透明悬浊液。第四步：溶液反应八分钟后取出样品，用超纯水冲洗样品表面除去表面吸附的CdS颗粒，然后用氮气枪将样品吹干。
步骤七：窗口层(ZnO/ITO)的制备。
通过磁控溅射法在上述样品上沉积本征氧化锌(i-ZnO)和氧化铟锡(ITO)做窗口层材料。磁控溅射仪溅射i-ZnO，溅射功率80W，纯氩气环境，气压为0.5Pa，膜层厚度50nm。溅射ITO的溅射功率为60W，纯氩气环境溅射气压为0.5Pa，膜层厚度200nm。
步骤八：电极(Ni/Al)的制备。
电池的阴极由金属Ni和Al组成，通过热蒸镀法制备。Ni和Al的厚度分别为50nm和500nm。
根据以上工艺制备的铜锌锡硫前驱体膜层和吸收膜层均无杂相，吸收层材料结晶度 高，形貌好，制备得到的铜锌锡硫太阳能电池能量转化效率为10.9％。
实施示例二：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMF通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物Sn(DMF) 2Cl 4。
步骤三：前驱体溶液的制备。量取8mL DMSO至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.626g(4mmol)步骤二中制备的锡配合物Sn(DMF) 2Cl 4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
实施示例三：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMSO通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次,烘干，得目标产物Sn(DMSO) 4Cl 4。
步骤三：前驱体溶液的制备。量取8mLDMF至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物Cu(Tu) 3Cl，1.667g(4mmol)步骤二中制备的锡配合物Sn(DMSO) 4Cl 4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
实施示例四：
步骤一：铜配合物的制备。此步骤操作方法同实施示例一。
步骤二：称取12.53克四氯化锡至圆底烧瓶中，将瓶口密封，取50ml DMF通过注射器注射至瓶中，两种物质接触后反应剧烈，生成大量白色沉淀。反应完成后，过滤反应液得白色沉淀，并用乙醇洗涤多次，烘干，得目标产物锡配合物Sn(DMF) 2Cl 4。
步骤三：前驱体溶液的制备。量取8mLDMF至试剂瓶中，称取2.0g(6.12mmol)步骤一中制备的铜配合物，1.626g(4mmol)步骤二中制备的锡配合物Sn(DMF) 2Cl 4，0.734g(4mmol)乙酸锌和0.2g硫脲加入试剂瓶中并在室温下搅拌至完全溶解。
步骤四至步骤八：操作方法同实施示例一。
本发明实施例提供了四种全新的制备高效CZTS太阳能电池的前驱体溶液的制备方法，即通过使用金属配合物作为前驱体化合物配制的前驱体溶液，制备结晶质量高，薄 膜形貌好，无杂质相的铜锌锡硫薄膜吸光材料，制备出高效率的铜锌锡硫太阳能电池。图1和图2分别为铜配合物和锡配合物的实物照片，经元素分析仪分析其化学组分分别为Cu(Tu) 3Cl和Sn(DMF) 2Cl。
图3、图4分别为基于以上两种金属配合物在DMSO和DMF溶剂中配制的前驱体溶液的实物照片，可以观察到两种溶液均澄清透明无沉淀和杂质产生，且稳定性好，表明其溶液质量高。
图5和图6为两种前驱体溶液经旋涂退火形成的前驱体薄膜的X射线衍射图谱，两个前驱体薄膜在衍射角2-Theta＝28.5，47.3，56.1度处均出现微弱的衍射峰，这些衍射峰分别对应铜锌锡硫相(CZTS)的(112)，(220)，(312)晶面(PDF#26-0575)，表明两组前驱体膜中均有CZTS相生成。图9和图10为前驱体薄膜的拉曼图谱，两个前驱体薄膜在拉曼位移为337cm -1处均出现明显的拉曼振动峰，对应于CZTS相。这两种表征手段都表明了前驱体薄膜中仅存在单一的铜锌锡硫物相，无其他杂质相，这有利于薄膜的后续生长和结晶。图7和图8为为两种前驱体薄膜硒化反应形成的铜锌锡硫硒吸收层薄膜的X射线衍射图谱，从图中可以看出两个铜锌锡硫硒吸收层薄膜在2-Theta＝27.1，45.0，53.4处均出现强衍射峰，这些衍射峰分别对应铜锌锡硒相(CZTSe)的(112)，(204)，(312)晶面，表明硒化后的吸收层薄膜均为CZTSe相，无其他杂相可观测到。
图11和图12为铜锌锡硫硒吸收层薄膜的拉曼图谱，从图中可以看出，两个前驱体薄膜在拉曼位移为172，193，231cm -1处均出现明显的拉曼振动峰，对应于铜锌锡硒相(CZTSe)，无其他杂质相的拉曼振动峰可观察到。这表明了制备的吸收层薄膜为高质量的铜锌锡硫硒薄膜。结合图13，14，15和16中观察到的的结晶度高，平整致密，无杂相的吸收层薄膜的扫描电镜照片，进一步表明实例制备的吸收层薄膜质量高。将两组吸光膜层制备成太阳能电池器件并对其进行光伏性能测试，它们的电压-电流特性曲线如图17，18所示，两个器件的光电转换效率均超过10％，达到国际先进水平。
综上，本发明的技术方案制备了稳定澄清透明的高质量前驱体溶液，并将其应用于铜锌锡硫硒薄膜材料和光伏器件制备，最终，得到了结晶质量高，形貌好，无杂相的铜锌锡硫硒薄膜材料和能量转化效率超过10％的光伏器件，表明该发明显著的先进性。
以上所述仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (10)

  1. 一种铜锌锡硫太阳能电池的前驱体溶液，其特征在于：以二甲基亚砜DMSO或N,N-二甲基甲酰胺DMF为溶剂，前驱体化合物为溶质配制；所述前驱体化合物由金属配合物、金属盐和硫脲组成，其中，所述金属配合物为铜盐与硫脲或硫脲衍生物形成的铜配合物、锡盐与DMF或DMSO形成的锡配合物，金属盐为二价锌盐；将以上前驱体化合物溶解在DMSO或DMF溶剂中得到稳定、澄清透明的前驱体溶液。
  2. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述铜配合物为铜盐与硫脲或硫脲的衍生物形成的配合物，包括：卤素铜盐与硫脲形成的配合物Cu(Tu) 3X，其中X为包括F、Cl、Br、I在内的卤族元素，所形成的铜配合物，包括：Cu(Tu) 3Cl，[Cu 2(Tu) 6]Cl 2·2H 2O,Cu(Tu) 3Br；还包括卤素铜盐与硫脲衍生物形成的配合物：Cu(DMTu) 3Br，Cu(TMTu) 3Cl，[Cu(ETu) 2Br] 2，其中DMTu为N,N-二甲基硫脲，TMTU为四甲基硫脲，ETu为乙撑硫脲；还包括硝酸铜盐与硫脲形成的配合物Cu 4(Tu) 10(NO 3)·Tu·3H 2O。
  3. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述锡配合物选自Sn(X) yCl 4，Sn(X) yF 4,Sn(X) yBr 4,Sn(X) yI 4,Sn(X) y(CH 3COO) 4中的一种或多种，X选自DMSO、DMF、乙醇、N-甲基吡咯烷酮中的一种，y为大于零的自然数。
  4. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述锌盐为二价锌的化合物，包括但不限于卤素锌盐、乙酸锌、硝酸锌、硫酸锌。
  5. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体溶液中，硫脲物质的量：铜元素的物质的量不大于1。
  6. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体化合物中：
    铜元素的物质的量：锡元素的物质的量为(1.5～2.5)：1；
    锌元素物质的量：锡元素的物质的量为(0.9～1.5)：1；
    硫元素物质的量：铜、锡与锌元素物质的量之和为(1.0～6.0)：1。
  7. 根据权利要求1所述的铜锌锡硫太阳能电池的前驱体溶液，其特征在于：所述前驱体溶液中：
    铜元素在溶液中浓度为0.05mol/L～5mol/L；
    锡元素在溶液中浓度为0.05mol/L～5mol/L；
    锌元素在溶液中浓度为0.05mol/L～5mol/L；
    硫元素在溶液中浓度为0.15mol/L～5mol/L。
  8. 根据权利要求1-7任一所述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，其特征在于：制备前驱体溶液的具体方法为分步制备法：以DMSO或DMF为溶剂，将铜配合物和硫脲溶解在溶剂中制备溶液一；将锡配合物和锌盐溶解在溶剂中制备溶液二；将溶液一和溶液二混合得到澄清透明的前驱体溶液。
  9. 根据权利要求8所述的铜锌锡硫太阳能电池的前驱体溶液的制备方法，其特征在于：铜配合物、锡配合物的制备方法为：
    合成铜配合物：将硫脲溶解在去离子水中，待硫脲完全溶解后将铜盐加入溶液中，所加入的硫脲与铜盐的物质的量之比为3:1，反应过程溶液温度为70摄氏度；溶解后，将溶液过滤，静置，缓慢冷却，目标产物铜配合物晶体从溶液中析出，取出上述晶体产物并烘干；
    合成锡配合物：取四价锡盐于圆底烧瓶中，密封瓶口，取有机化合物溶剂DMF或DMSO注入瓶中，其中溶剂中有机化合物与锡盐物质的量之比为2～20；锡盐与DMF或DMSO溶剂反应生成大量白色沉淀，用乙醇将沉淀清洗干净，烘干即得相应目标产物锡配合物。
  10. 根据权利要求1-7任一所述的一种铜锌锡硫太阳能电池的前驱体溶液应用于制备铜锌锡硫太阳能电池，其特征在于：铜锌锡硫太阳能电池的制备方法包括以下步骤：
    (1)将制备获得的前驱体溶液旋涂在钼玻璃上，加热退火生成铜锌锡硫前驱体薄膜；
    (2)将所述前驱体薄膜在Se的气氛中加热进行硒化反应，以Se原子部分或者全部取代S原子生成铜锌锡硫Se薄膜材料；
    (3)将硒化反应后的铜锌锡硫Se膜取出并用超纯水浸泡后置于含有氨水、硫酸镉和硫脲溶液的水夹套烧杯中，在加热情况下进行反应，在铜锌锡硫Se膜表面沉积一层CdS；
    (4)通过磁控溅射技术在步骤(3)的样品表面依次溅射ZnO和ITO作为窗口层；
    (5)通过热蒸镀方法在步骤(4)获得的样品表面蒸镀金属Ni和Al作为阴极。
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