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 PDFInfo
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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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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
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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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| CN101861654A (en) * | 2007-07-09 | 2010-10-13 | 塔林科技大学 | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
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| CN101861654A (en) * | 2007-07-09 | 2010-10-13 | 塔林科技大学 | Photovoltaic cell based on zinc oxide nanorods and method for making the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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