CN104167294A - In2S3/CuInS2 thin layer sensitization broadband semiconductor photoanode and preparation method for the same - Google Patents

In2S3/CuInS2 thin layer sensitization broadband semiconductor photoanode and preparation method for the same Download PDF

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CN104167294A
CN104167294A CN201410302030.8A CN201410302030A CN104167294A CN 104167294 A CN104167294 A CN 104167294A CN 201410302030 A CN201410302030 A CN 201410302030A CN 104167294 A CN104167294 A CN 104167294A
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broadband semiconductor
thin layer
cuins
solution
broadband
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徐雪青
安萍
梁柱荣
徐刚
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

The invention discloses an In2S3/CuInS2 thin layer sensitization broadband semiconductor photoanode, consisting of a conductive substrate, a broadband semiconductor film layer and an In2S3/CuInS2 thin layer. A broadband semiconductor film layer is deposed on the surface of the conductive substrate to construct a broadband semiconductor film electrode; an In2S3 thin layer and a CuInS2 thin layer successively wrap the surface of the broadband semiconductor film electrode; the thickness of the In2S3 film is between 1-5nm, and the thickness of the CuInS2 film is between the 2-15nm; and a constant ion layer adsorption reaction method is adopted. The preparation method for the In2S3/CuInS2 thin layer sensitization photoanode structure is simple in the technology, can control the size of the grain through controlling the concentration of the solution and the sensitization times, can optimize the CuInS2 chemical stoichiometric ratio, and can reduce the material defect. The introduced buffer layer In2S3 can effectively inhibit electron compositing, which is beneficial for the injection of the electrons, can effectively avoid the pollution caused by the Cu in the CuInS2 diffusing to TiO2 and the change of the stoichiometric rate, and has positive meaning for improving photoelectric conversion rate of the CuInS2 semiconductor nanocrystalline sensitization solar battery.

Description

A kind of In 2s 3/ CuInS 2broadband semiconductor light anode of thin layer sensitization and preparation method thereof
Technical field
The invention belongs to technical field of solar utilization technique, relate in particular to the research field of the solar energy electrochemical cell of the broadband semiconductor light anode based on thin layer sensitization.
Technical background
Photoelectrochemical cell based on the sensitized porous nanocrystalline broadband semiconductor light anode of thin layer has three-dimensional body junction structure, and lower to fault in material requirement, preparation technology is simple, with low cost, has been subject to various countries researcher's extensive concern since its invention.CuInS wherein 2optical absorption coefficient is high (reaches 6 * 10 5cm -1), conduction band position and nano-TiO 2deng broadband semiconductor, match, energy gap (Eg is 1.50eV) approaches the best energy gap (1.45eV) of solar cell material, and raw material is low compared with horn of plenty toxicity, and has good photochemical stability, is desirable photosensitive materials.
CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization comprises atomic layer deposition method, chemical bath deposition method and continuous ionic layer adsorption reaction method etc., wherein continuous ionic layer adsorption reaction method have with low cost, hold manageable feature.But the CuInS that adopts traditional sheath adsorption reaction method to prepare 2stoichiometric proportion is difficult to control, and material internal defect is many, and electron recombination is comparatively serious, and the quantum efficiency of photoelectrochemical cell is lower.In addition CuInS, 2in Cu +ion is easily diffused into broadband semiconductor interstitial void, causes broadband semiconductor/CuInS 2the defect at interface and electron recombination.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of In is provided 2s 3/ CuInS 2broadband semiconductor light anode of thin layer sensitization and preparation method thereof, at broadband semiconductor rete and CuInS 2between one deck In is set 2s 3resilient coating, to stop Cu +the diffusion of ion, reduce the compound of interface electronics.
Another object of the present invention is to provide the above-mentioned In of preparation 2s 3/ CuInS 2the method of the broadband semiconductor light anode of thin layer sensitization.
In of the present invention 2s 3/ CuInS 2the broadband semiconductor light anode of thin layer sensitization, is characterized in that by conductive substrate, broadband semiconductor rete and In 2s 3/ CuInS 2thin layer forms, and has broadband semiconductor film to form broadband semiconductor membrane electrode, at the successively coated In in broadband semiconductor membrane electrode surface at conductive substrate surface deposition 2s 3with CuInS 2thin layer, In 2s 3thickness between 1-5nm, CuInS 2thickness between 2-15nm.Described broadband semiconductor rete, can be the nanocrystalline broadband semiconductor rete of porous, or fine and close nanocrystalline broadband semiconductor rete, the preferably nanocrystalline broadband semiconductor rete of porous; Broadband semiconductor is selected from TiO 2, ZnO and SnO 2in one or more.
Described In 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, adopts improved continuous ionic layer adsorption reaction method, on broadband semiconductor film surface, successively deposits In xs and Cu ys, and In-S frequency of depositing is more than the precipitation number of Cu-S, then by carry out vacuum heat in sulphur atmosphere, obtains In 2s 3/ CuInS 2thin layer sensitization broadband semiconductor light anode.
Specifically comprise the steps:
(1) first broadband semiconductor membrane electrode is flooded 30-360 second in indium ion solution;
(2) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary indium ion in surface, dry up;
(3) the broadband semiconductor membrane electrode that has adsorbed indium ion is flooded 30-240 second in sulphion solution;
(4) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(5) repeating step (1) to (4) is 3-15 time;
(6) then broadband semiconductor membrane electrode is flooded 30-240 second in copper ion solution;
(7) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary copper ion in surface, dry up;
(8) then the broadband semiconductor membrane electrode that has adsorbed copper ion is flooded 20-240 second in sulphion solution;
(9) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(10) repeating step (6) to (9) is 2-7 time;
(11) heat treatment: above-mentioned broadband semiconductor membrane electrode is heat-treated in sulphur or hydrogen sulfide atmosphere under vacuum condition.
Heat-treating methods is: vacuum degree control is 1 * 10 -4between Pa～100Pa, preferably 1 * 10 -3pa～1 * 10 -2between Pa, heat treatment temperature is between 450 ℃-550 ℃, and heat treatment time is between 10 minutes-60 minutes.
Described heat treatment also can be carried out rapid thermal annealing under vacuum condition, and vacuum degree control is 1 * 10 -4pa～1 * 10 - 2between Pa, heat treatment temperature is between 450 ℃-550 ℃, and heat treatment time is between 2 minutes-10 minutes.
The improved continuous ionic layer of said employing adsorption reaction method is successively to deposit In on broadband semiconductor film surface xs and Cu ys, then in vacuum sulphur atmosphere, heat treatment makes part In xs and Cu ys reaction generates CuInS2, and another part In xs changes into resilient coating In 2s 3.Due to the frequency of depositing of In-S frequency of depositing more than Cu-S, avoided departing from of stoichiometric proportion that the volatilization of indium causes, and can be at broadband semiconductor/CuInS 2interface obtains In 2s 3resilient coating; By the frequency of depositing of accurate control In-S and Cu-S, can control In 2s 3thickness and CuInS 2crystallite dimension and stoichiometric proportion.The said vacuum heat of carrying out in sulphur atmosphere is in order to supplement the sulphur component of high-temperature heat treatment process loss.
Described indium ion solution is the aqueous solution of inidum chloride, indium acetate, indium nitrate or indium sulfate, or any one in its alcoholic solution.
Described copper ion solution is the aqueous solution of stannous chloride, copper chloride, Schweinfurt green, copper sulphate or any one in its alcoholic solution.
Said sulphion solution can be the cushioning liquid of vulcanized sodium, and pH value of buffer solution is between 8-12.Or be the cushioning liquid of thioacetamide, pH value of buffer solution is between 2-6, and solution temperature is between 40 ℃-90 ℃.Or be the cushioning liquid of thiocarbamide, pH value of buffer solution is between 8-12, and solution temperature is between 40 ℃-90 ℃.
The concentration of described indium ion solution is between 50mmol/L to 200mmol/L, and the concentration of copper ion is between 5mmol/L to 50mmol/L, and the concentration of sulphion is between 10mmol/L to 100mmol/L.The concentration of indium ion will be higher than the concentration of copper ion and sulphion, because copper belongs to soft acid, indium belongs to hard acid, chalcogen soft base, and according to hard and soft acid and base principle, indium is difficult is combined with sulphur, thereby indium ion concentration is high is conducive to adsorb indium ion, optimization stoichiometric proportion.
Compared with the existing technology, tool has the following advantages in the present invention:
1, In of the present invention 2s 3/ CuInS 2the broadband semiconductor light anode of thin layer sensitization, at broadband semiconductor and CuInS 2in has been introduced at interface 2s 3resilient coating, can effectively avoid CuInS 2in Cu ion be diffused in broadband semiconductor lattice and pollution and the defect brought can suppress interface electron recombination effectively, improve the quantum efficiency of photoelectrochemistrpool pool.
2, In of the present invention 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, adopts improved sheath adsorption reaction method, on broadband semiconductor film surface, successively deposits In xs and Cu ys, then in vacuum sulphur atmosphere, heat treatment makes part In xs and Cu ys reaction generates CuInS 2, and another part In xs changes into resilient coating In 2s 3, avoided departing from of stoichiometric proportion that the volatilization of indium causes, by the frequency of depositing of accurate control In-S and Cu-S, control In 2s 3thickness and CuInS 2crystallite dimension and stoichiometric proportion, realize one-step method and obtain In 2s 3/ CuInS 2the broadband semiconductor of sensitization, easy and simple to handle, and be difficult for introducing impurity.
In of the present invention 2s 3/ CuInS 2not only preparation technology is easy for thin layer sensitization light anode construction, can control grain size by controlling solution concentration and sensitization number of times, optimizes CuInS 2stoichiometric proportion, reduce fault in material, and the resilient coating In introducing 2s 3can effectively suppress electron recombination, be conducive to electronic injection, and can effectively avoid because of CuInS 2in Cu be diffused into TiO 2and the variation of the pollution bringing and its stoichiometric proportion, therefore, the present invention is for optimizing CuInS 2stoichiometric proportion, effectively suppresses interface electron recombination, improves based on CuInS 2the quantum efficiency of the photoelectrochemistrpool pool of sensitization broadband semiconductor light anode has positive effect.
Accompanying drawing explanation
Fig. 1 is embodiment of the present invention 1In 2s 3/ CuInS 2thin layer sensitized nanocrystalline TiO 2the absorption spectrum of light anode, wherein In acu bin a, b represent respectively the frequency of depositing of In-S and Cu-S.In figure, show In 2s 3/ CuInS 2thin layer sensitization light anode ABSORPTION EDGE is in 820nm left and right, with CuInS 2energy gap match.
Fig. 2 is that the embodiment of the present invention 1 is based on In 2s 3/ CuInS 2thin layer sensitized nanocrystalline TiO 2the J-V curve of the solar cell of light anode, wherein J is density of photocurrent, V is photovoltage, In in this figure 2s 3/ CuInS 2thin layer sensitized nanocrystalline TiO 2that the photoelectric conversion efficiency of the solar cell that light anode is prepared is the highest is 0.92% (In10Cu5), and battery open circuit voltage is 0.35V, and short circuit current is 8.49mA/cm 2, fill factor, curve factor is 0.31.
Embodiment
Below in conjunction with drawings and Examples, content of the present invention is further described
In 2s 3/ CuInS 2the optical absorption characteristics of the broadband semiconductor light anode of sensitization adopts ultraviolet-visible-near infrared spectrometer to measure; With In 2s 3/ CuInS 2the broadband semiconductor light anode of sensitization is work electrode, Cu 2s electrode is to electrode, and the water base many sulphur electrolyte of take is electrolyte, with Dupont tM 1702 PURs (thickness 50 μ m) sealant is assembled into solar cell, measures the J-V curve of solar cell, calculates photoelectric conversion efficiency of the solar battery.
Embodiment 1
By nano titania slurry (nano-TiO 2average grain diameter is 15nm, and voidage is 65%) in the mode of blade coating, be coated on fluorine doped tin oxide transparent conducting glass substrate, at 450 ℃, heat treatment is 30 minutes, obtains nano-TiO 2light anode, thickness is 5 microns.Then prepare in accordance with the following steps In 2s 3/ CuInS 2the nano-TiO of thin layer sensitization 2light anode:
(1) first by nano-TiO 2in the inidum chloride aqueous solution that light anode is 100mmol/L in concentration, flood 120 seconds;
(2) with distilled water, wash nano-TiO 2light anode, removes the unnecessary In in surface 3+ion, dries up;
(3) nano-TiO of indium ion will have been adsorbed 2in the vulcanized sodium buffer solution that light anode is 80mmol/L in concentration, flood 180 seconds, pH value of buffer solution is 10,60 ℃ of solution temperatures;
(4) with distilled water washing broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(5) repeating step (1) is to (4) 10 times
(6) in the aqueous solution of the stannous chloride that is then 10mmol/L by broadband semiconductor membrane electrode in concentration, flood 60 seconds;
(7) with distilled water washing broadband semiconductor membrane electrode, remove the unnecessary copper ion in surface, dry up;
(8) in the vulcanized sodium buffer solution that is then 80mmol/L by the broadband semiconductor membrane electrode that has adsorbed copper ion in concentration, flood 180 seconds, pH value of buffer solution is 10,60 ℃ of solution temperatures;
(9) with distilled water washing broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(10) repeating step (6) is to (9) 5 times;
(11) heat treatment: above-mentioned broadband semiconductor membrane electrode is heat-treated in sulphur atmosphere under vacuum condition, and vacuum degree control is 6 * 10 -2pa, heat treatment temperature is at 520 ℃, and heat treatment time is 30 minutes.
Prepared In 2s 3thickness is 3nm, CuInS 2thickness is 10nm, this In 2s 3/ CuInS 2thin layer sensitization nano-TiO 2the photoelectric conversion efficiency of solar cell is about 0.92% (as Fig. 2).
Embodiment 2
What in the step (1) of preparation process, adopt as different from Example 1 is the methanol solution of the indium sulfate of 50mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 3
What in the step (1) of preparation process, adopt as different from Example 1 is the ethanolic solution of the indium nitrate of 200mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 1.1%.
Embodiment 4
What in the step (1) of preparation process, adopt as different from Example 1 is the ethanolic solution of the indium acetate of 200mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 1.0%.
Embodiment 5
What in the step (6) of preparation process, adopt as different from Example 1 is the ammonia spirit of the stannous chloride of 5mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.7%.
Embodiment 6
What in the step (6) of preparation process, adopt as different from Example 1 is the aqueous solution of the copper sulphate of 50mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.6%.
Embodiment 7
What in the step (6) of preparation process, adopt as different from Example 1 is the aqueous solution of the Schweinfurt green of 20mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 8
What in the step (6) of preparation process, adopt as different from Example 1 is the ethanolic solution of the copper nitrate of 30mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 9
What in the step (6) of preparation process, adopt as different from Example 1 is the ethanolic solution of the Schweinfurt green of 10mmol/L.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 1.1%.
Embodiment 10
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the cushioning liquid of the vulcanized sodium of 40mmol/L, and the pH value of cushioning liquid is 8, and solution temperature is 25 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 2.0%.
Embodiment 11
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the cushioning liquid of the vulcanized sodium of 100mmol/L, and the pH value of cushioning liquid is 12, and solution temperature is 80 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 2.3%.
Embodiment 12
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the cushioning liquid of the thioacetamide of 50mmol/L, and the pH value of cushioning liquid is 3, and solution temperature is 60 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 1.0%.
Embodiment 13
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the cushioning liquid of the thioacetamide of 10mmol/L, and the pH value of cushioning liquid is 6, and solution temperature is 90 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.7%.
Embodiment 14
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the cushioning liquid of the thioacetamide of 100mmol/L, and the pH value of cushioning liquid is 2, and solution temperature is 40 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 15
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the thiocarbamide buffer soln of 80mmol/L, and the pH value of cushioning liquid is 10, and solution temperature is 60 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.9%.
Embodiment 16
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the thiocarbamide buffer soln of 10mmol/L, and the pH value of cushioning liquid is 12, and solution temperature is 90 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 17
What in the step (3) of preparation process and step (8), adopt as different from Example 1 is the thiocarbamide buffer soln of 100mmol/L, and the pH value of cushioning liquid is 8, and solution temperature is 40 ℃.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.7%.
Embodiment 18
In the step (5) of preparation process, number of repetition is 15 times as different from Example 1, and in step (10), number of repetition is 7.The In obtaining 2s 3thickness is 5nm, CuInS 2thickness is 15nm, with the In of smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.6%.
Embodiment 19
In the step (5) of preparation process, number of repetition is 3 times as different from Example 1, and in step (10), number of repetition is 2.The In obtaining 2s 3thickness is 1nm, CuInS 2thickness is 2nm, with the In of smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.1%.
Embodiment 20
In the step (1) of preparation process, (3), (6), (8), dip time is all 30 seconds as different from Example 1.The In obtaining 2s 3thickness is 1nm, CuInS 2thickness is 2nm, with the In of smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.1%.
Embodiment 21
In the step (1) of preparation process, (3), dip time is all 360 seconds as different from Example 1, and in step (6), (8), dip time is all 240 seconds.The In obtaining 2s 3thickness is 4.5nm, CuInS 2thickness is 15nm, with the In of smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.2%.
Embodiment 22
In the step (11) of preparation process, heat treatment temperature is 550 ℃ as different from Example 1, and the time is 10 minutes.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.9%.
Embodiment 23
In the step (11) of preparation process, heat treatment temperature is 450 ℃ as different from Example 1, and the time is 60 minutes.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.7%.
Embodiment 24
As different from Example 1 in the step (11) of preparation process in heat treatment process vacuum degree control at 100Pa.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.6%.
Embodiment 25
As different from Example 1 in the step (11) of preparation process in heat treatment process vacuum degree control 1 * 10 -4pa.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 3.8%.
Embodiment 26
As different from Example 1, in the step (11) of preparation process, rapid thermal annealing is carried out in heat treatment under vacuum condition, and vacuum degree control is 1 * 10 -4pa, heat treatment temperature is at 550 ℃, and heat treatment time was at 2 minutes.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 3.3%.
Embodiment 27
As different from Example 1, in the step (11) of preparation process, rapid thermal annealing is carried out in heat treatment under vacuum condition, and vacuum degree control is 1 * 10 -2pa, heat treatment temperature is at 450 ℃, and heat treatment time is 10 minutes.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.8%.
Embodiment 28
In the step (11) of preparation process, heat treatment process is carried out in hydrogen sulfide atmosphere as different from Example 1.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.5%.
Embodiment 29
Adopt as different from Example 1 porous nano SnO 2light anode (nano SnO 2average grain diameter is 15nm, and voidage is 60%).In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.9%.
Embodiment 30
Adopt as different from Example 1 fine and close nano-TiO 2light anode.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.2%.
Embodiment 31
Adopt as different from Example 1 fine and close nano-ZnO light anode.In with smooth anode assembling of the present invention 2s 3/ CuInS 2the photoelectric conversion efficiency of thin layer sensitized nanocrystalline solar cell is about 0.1%.

Claims (7)

1. an In 2s 3/ CuInS 2the broadband semiconductor light anode of thin layer sensitization, is characterized in that by conductive substrate, broadband semiconductor rete and In 2s 3/ CuInS 2thin layer forms, and has broadband semiconductor rete to form broadband semiconductor membrane electrode, at the successively coated In in broadband semiconductor membrane electrode surface at conductive substrate surface deposition 2s 3with CuInS 2thin layer, In 2s 3thickness between 1-5nm, CuInS 2thickness between 2-15nm.
2. In as claimed in claim 1 2s 3/ CuInS 2the broadband semiconductor light anode of thin layer sensitization, is characterized in that described broadband semiconductor rete is the nanocrystalline broadband semiconductor rete of porous, and described broadband semiconductor is selected from TiO 2, ZnO and SnO 2in a kind of.
3. In as claimed in claim 1 or 2 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, is characterized in that adopting continuous ionic layer adsorption reaction method, on broadband semiconductor film surface, successively deposits In xs and Cu ys, and In-S frequency of depositing is more than the precipitation number of Cu-S, then by carry out vacuum heat in sulphur or hydrogen sulfide atmosphere, obtains In 2s 3/ CuInS 2thin layer sensitization broadband semiconductor light anode.
4. In as claimed in claim 3 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, is characterized in that specifically comprising the steps:
(1) first broadband semiconductor membrane electrode is flooded 30-360 second in indium ion solution;
(2) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary indium ion in surface, dry up;
(3) the broadband semiconductor membrane electrode that has adsorbed indium ion is flooded 30-240 second in sulphion solution;
(4) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(5) repeating step (1) to (4) is 3-15 time;
(6) then broadband semiconductor membrane electrode is flooded 30-240 second in copper ion solution;
(7) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary copper ion in surface, dry up;
(8) then the broadband semiconductor membrane electrode that has adsorbed copper ion is flooded 20-240 second in sulphion solution;
(9) with solvent wash broadband semiconductor membrane electrode, remove the unnecessary sulphion in surface, and dry up;
(10) repeating step (6) to (9) is 2-7 time;
(11) heat treatment: above-mentioned broadband semiconductor membrane electrode is heat-treated in sulphur or hydrogen sulfide atmosphere under vacuum condition.
5. according to claim 4 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, it is characterized in that described indium ion solution is the aqueous solution of inidum chloride, indium acetate, indium nitrate or indium sulfate, or any one in its alcoholic solution, concentration is between 50mmol/L to 200mmol/L.
6. according to claim 4 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, is characterized in that described copper ion solution is the aqueous solution of stannous chloride, copper chloride, Schweinfurt green, copper sulphate or any one in its alcoholic solution, and concentration is between 5mmol/L to 50mmol/L.
7. according to claim 4 2s 3/ CuInS 2the preparation method of the broadband semiconductor light anode of thin layer sensitization, is characterized in that sulphion solution is the cushioning liquid of vulcanized sodium, and pH value of buffer solution is between 8-12, and solution temperature is between 25 ℃-80 ℃; Or be the cushioning liquid of thioacetamide, pH value of buffer solution is between 2-6, and solution temperature is between 40 ℃-90 ℃; Or be the cushioning liquid of thiocarbamide, pH value of buffer solution is between 8-12, and solution temperature is between 40 ℃-90 ℃; Concentration is all between 10mmol/L to 100mmol/L.
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CN104638064A (en) * 2015-01-26 2015-05-20 西南交通大学 Preparation method of ZnO-CuInS2 heterogeneous core-shell structure nanorod array
CN111689512A (en) * 2019-03-13 2020-09-22 中国科学院上海高等研究院 In-doped Cu-S-based thermoelectric material and preparation method thereof
CN113436895A (en) * 2021-06-17 2021-09-24 北方民族大学 Method for preparing compact PbS quantum dot film by taking fatty acid lead as lead source

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