CN104143444A - Multi-level indium tin oxide nanowire array composite material, preparing method thereof and application in solar cell - Google Patents
Multi-level indium tin oxide nanowire array composite material, preparing method thereof and application in solar cell Download PDFInfo
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Abstract
The invention discloses a multi-level indium tin oxide nanowire array composite material, a preparing method thereof and an application in a solar cell. The multi-level indium tin oxide nanowire array composite material comprises a multi-level indium tin oxide nanowire array which is developed on a conducting substrate and is wrapped by a Cu2S shell layer. The preparing method comprises the following steps that firstly, gold nanoparticles serve as the catalyst, and indium tin oxide nanowires are deposited and developed on the conducting substrate in sequence according to the number of levels through the chemical vapor deposition method; secondly, the nanowire array is wrapped by the Cu2S shell layer through one of the first method, the second method and the third method, wherein the first method is a chemical bath deposition method in which the conducting substrate is wrapped by a CdS shell layer and then the CdS shell layer is transformed into the Cu2S shell layer through the ion exchange method, the second method is a continuous ionic layer adsorption method for performing wrapping, and the third method is a magnetron sputtering method for performing wrapping; thirdly, under the inert atmosphere, the multi-level indium tin oxide nanowire array composite material is obtained through burning. The Cu2S@ITO-X nanowire array serves as the counter electrode material, the performance of the solar cell assembled through the counter electrode material is obviously superior to the performance of a solar cell with the precious metal Pt or Au and transition metal chalcogen compound as the counter electrode material.
Description
Technical field
The present invention relates to a kind of multi-stage oxidizing indium stannum nanowire array composite material and preparation method thereof and application in solar cell, belong to technical field of solar.
Background technology
Solar energy gets more and more people's extensive concerning as a kind of clean regenerative resource, as the solar cell of electrooptical device, has also obtained research widely.As market-oriented the earliest solar cell, up to the present silica-based solar cell relies on its high electricity conversion and stability, still most market shares have been occupied, but be subject to the restriction of production technology, the production cost of silica-based solar cell is too high, cannot match in excellence or beauty with traditional fossil energy.Therefore, new solar battery structure and cheaply production technology become the emphasis of solar cell research.
Liquid phase method in the synthetic method of light-sensitive material has without high-vacuum apparatus and high temperature preparation process, can significantly reduce the production cost of material, wherein quantum dot sensitized solar cell is the synthetic solar cell of liquid phase method as a kind of light-sensitive material, when structurally having used for reference DSSC, the inorganic semiconductor quantum dot of usining replaces organic dye molecule as light absorbent, not only can significantly reduce production costs, rely on quantum size effect and the polyelectron priming effect of inorganic-quantum-dot simultaneously, make its theoretical light photoelectric transformation efficiency bring up to 44% from 31%, become the solar cell types that a class has Commercial Prospect very much.Current research shows, the deficiency to many sulphur of electrode catalyst electrolyte generation reduction reaction ability in quantum dot sensitized solar cell is one of key factor of restriction cell photoelectric transformation efficiency lifting, from the reaction of battery performance curve, is that fill factor, curve factor is lower.Initial stage is precious metals pt or Au catalyst for quantum dot sensitized solar cell to electrode material, and the one-tenth that the use of noble metal catalyst has not only increased quantum dot sensitized solar cell greatly produces cost, and its catalytic performance is also undesirable.To the research of electrode then adopt and take the non-precious metal catalyst that transient metal chalcogenide compound is representative, comprise Cu subsequently
2s, PbS, CoS, NiS and quaternary compound Cu
2znSnS
4, Cu
2znSnSe
4deng.Because the ability of such many sulphur of electrode catalyst catalysis electrolyte generation reduction reaction is stronger, thereby show than the better catalytic performance of noble metal catalyst.Research by electrochemical impedance spectroscopy is with Cu
2s is that example is found, obvious decline has occurred the resistance between in running order counter electrode of battery material and electrolyte (solid liquid interface), reaches and CTO glass and Cu
2between S (solid solid interface) and the suitable level of surface resistance of CTO glass self, after making, both can significantly affect the transfer to electrode place electric charge equally, thereby affect the electricity conversion of battery.Therefore, how the relation between three kinds of resistance of balance improves the catalytic performance of electrode material and then obtains efficient quantum dot sensitized solar cell and still exists very large challenge.
Therefore, provide a kind of simply, cheaply to electrode material and technology of preparing thereof, and efficiently, be stably of great significance for quantum dot sensitized solar cell tool.
Summary of the invention
The object of this invention is to provide a kind of preparation method of multi-stage oxidizing indium stannum nanowire array composite material and the application in solar cell.
The invention provides a kind of multi-stage oxidizing indium stannum nanowire array (Cu
2s@ITO-X) composite material, it comprises the multi-stage oxidizing indium stannum nanowire array being grown in conductive substrates, on described multi-stage oxidizing indium stannum nanowire array, is enclosed with cuprous sulfide shell.
In above-mentioned composite material, the progression of described multi-stage oxidizing indium stannum nanowire array can be 1～5 grade, specifically can be 1～4 grade, 1 grade, 2 grades, 3 grades or 4 grades;
The length that described multi-stage oxidizing indium stannum nanowire array is every grade can be 1 micron～30 microns, specifically can be 5 microns～10 microns, 5 microns or 10 microns, and diameter can be 50 nanometer～300 nanometers, specifically can be 100 nanometer～120 nanometers, 100 nanometers or 120 nanometers.
" multistage " described in the present invention refers to the number of times that deposits successively tin indium oxide nano-wire array on the tin indium oxide nano-wire array of embryo deposit.
Described in the present invention, " tin indium oxide nano-wire array " is a kind of nano-wire array of disordered structure.
The thickness of described cuprous sulfide shell can be 5 nanometer～100 nanometers, specifically can be 30～60 nanometers or 50 nanometers;
Described conductive substrates can be indium oxide tin glass (ITO) or fluorine-doped tin oxide glass (FTO).
The present invention also provides the preparation method of described composite material, comprises the steps:
(1) take gold nano grain as catalyst, by chemical vapour deposition technique, in described conductive substrates, press progression deposition growing tin indium oxide nano-wire successively, obtain described multi-stage oxidizing indium stannum nanowire array;
(2) by following 1)-3) in method coated Cu on described multi-stage oxidizing indium stannum nanowire array described in any
2s shell:
1) by chemical bath deposition (CVD) method, coated CdS shell on described multi-stage oxidizing indium stannum nanowire array; Then by ion-exchange, described CdS shell is changed into Cu
2s shell;
2) by continuous ionic layer absorption (SILAR) method, coated Cu on described multi-stage oxidizing indium stannum nanowire array
2s shell;
3) by magnetron sputtering method, coated Cu on described multi-stage oxidizing indium stannum nanowire array
2s shell;
(3) under inert atmosphere, through calcining and obtain described composite material.
Above-mentioned preparation method, in step (1), the particle diameter of described gold nano grain can be 2～10 nanometers, specifically can be 5 nanometers;
The described multi-stage oxidizing indium stannum nanowire array indium source used of growing can be indium metal and/or indium oxide;
The described tin indium oxide nano-wire array Xi Yuan used that grows can be metallic tin and/or tin oxide;
The mol ratio of described indium source and described Xi Yuan can be 1～30:1, specifically can be 10:1.
Above-mentioned preparation method, in step (1), growth described multi-stage oxidizing indium stannum nanowire array He Xi source, indium source used is heated into gaseous state under the condition of 600～1000 ℃, can be 5～120 minutes heating time, as heated 10 minutes or 15 minutes at 800 ℃;
The growth course of described multi-stage oxidizing indium stannum nanowire array is carried out in crystallizing field, and the temperature of described crystallizing field can be 300～550 ℃, and growth time can be 5～120 minutes, as grown under the condition at 400 ℃ 10 minutes or growing under the condition of 400 ℃ 15 minutes.
Above-mentioned preparation method, step (2) 1) in,
The cadmium salt that described chemical bath deposition method is used can be at least one in cadmium acetate, caddy, cadmium sulfate and cadmium nitrate, specifically can be cadmium sulfate;
The sulfosalt that described chemical bath deposition method is used can be at least one in sulphur powder, thiocarbamide, thiosemicarbazides and thioacetamide, specifically can be thiocarbamide;
The temperature of described chemical bath deposition method can be 0～100 ℃, and the time can be 0.1～8 hour, specifically can under the condition of 65 ℃, deposit 11 minutes;
Described ion-exchange comprises the steps:
The multi-stage oxidizing indium stannum nanowire array of the coated CdS shell obtaining is transferred in the aqueous solution of mantoquita, through ion-exchange reactions, is about to described CdS shell and changes into Cu
2s shell;
Described mantoquita can be at least one in cuprous acetate, stannous chloride and cuprous sulfate, specifically can be stannous chloride;
The temperature of described ion-exchange reactions can be 5～90 ℃, and the time can be 0.5～60 minute, specifically can under the condition of 50 ℃, exchange 30 minutes;
Above-mentioned preparation method, step (2) 2) in,
Described continuous ionic layer absorption method comprises the steps:
Described multi-stage oxidizing indium stannum nanowire array is transferred in the mixed aqueous solution of mantoquita and sulfosalt, through the absorption of continuous ionic layer, on described multi-stage oxidizing indium stannum nanowire array, is coated Cu
2s shell;
Described mantoquita can be at least one in cuprous acetate, stannous chloride and cuprous sulfate, specifically can be stannous chloride;
Described sulfosalt can be at least one in vulcanized sodium, potassium sulfide and ammonium sulfide, specifically can be vulcanized sodium;
The temperature of described continuous ionic layer absorption method can be 5～50 ℃, and continuous adsorption number of times can be 1～20 time, and each time can be 0.5～5 minute, specifically can be under the reaction condition of 20 ℃ continuous adsorption 10 times, each 1 minute time;
Above-mentioned preparation method, step (2) 3) in,
Described magnetron sputtering method adopts radio frequency sputtering method;
The condition of described radio frequency sputtering method is as follows:
Power can be 100～300 watts, and sputtering pressure can be 3～10 millitorrs, and the time can be 200～2000 seconds, specifically can be at 150 watts, and under 3 millitorr conditions, sputter is 1000 seconds.
Above-mentioned preparation method, in step (4), the temperature of described calcining can be 200～500 ℃, and the time can be 10～60 minutes, specifically can under the condition of 300 ℃, calcine 30 minutes.
Multi-stage oxidizing indium stannum nanowire array composite material prepared by the present invention can be used as solar cell to electrode, described solar cell can be quantum dot sensitized solar cell or DSSC etc.In described multi-stage oxidizing indium stannum nanowire array composite material, branch-like multi-stage oxidizing indium stannum nanowire array and conductive substrates wherein form three-dimensional conductive network, what the electronics that makes the electrode collect can be exceedingly fast is injected in electrode catalyst, then utilizes and loads on the Cu with high-efficiency catalytic activity on conductive network
2therefore S catalyst carries out the reduction reaction of effective catalytic electrolysis matter, uses composite material of the present invention as to electrode, the plurality of advantages such as have that method is simple, cost is low, catalytic activity is high and steady in a long-term.
With other prior art comparisons, the present invention has following characteristics:
1, the branch-like multi-stage oxidizing indium stannum nanowire array that adopts chemical vapour deposition technique to prepare in the present invention, because the structure of its monocrystalline can be transmitted fast electronics and can not be subject to the inhibition of crystal boundary in nano wire; Due to the branch-like multilevel hierarchy of tin indium oxide nano-wire array, by it, as carrier, can improve greatly the load capacity of catalyst and then improve the catalytic efficiency to electrode simultaneously.
2, the present invention adopts Cu
2s as highly active to electrode catalyst, due to preparation Cu
2s continuously fine and close be coated on ITO surface and not with graininess, distribute, and has greatly improved the load capacity of catalyst and then has improved the catalytic efficiency to electrode.Owing to adopting the multi-stage oxidizing indium stannum nanowire array of conduction to replace traditional metallic substrates, as copper, make described electrode to be avoided by the slow problem of corrosion of many sulphur electrolyte, thereby there is better stability.
3, the prepared Cu of the inventive method
2s@ITO-X nano-wire array, owing to generating Cu by chemical bath deposition and ion-exchange process original position
2s, the interface between itself and ITO is very good.Multilevel Cu wherein
2s@ITO nano-wire array utilizes heavily doped P type semiconductor to contact with heavily doped N type semiconductor, can form good ohmic contact, is conducive to the injection of electronics; Be injected into Cu
2after S, due to this layer of Cu
2s thickness is in tens nanometers, and electronics is easy to through Cu
2s and arrive electrolyte interface, thus the series resistance in battery operated obviously reduced, the remarkable solar energy conversion efficiency that improves battery.
4, the Cu that uses the present invention to prepare
2s@ITO-X nano-wire array is as to electrode material, and the solar cell properties of its composition is obviously better than precious metals pt or Au and transient metal chalcogenide compound as the solar cell to electrode material.
Therefore the Cu that, prepared by the present invention
2s@ITO-X nano-wire array has huge potential using value in area of solar cell, Industrial Catalysis or other scientific domains.
Accompanying drawing explanation
Fig. 1 is embodiment 1 gained Cu
2s@ITO-3 nano-wire array and ITO nano-wire array and In
2o
3the powder x-ray diffraction spectrum of standard P DF card.
Fig. 2 (a) is the low power electron scanning micrograph of three grades of ITO nano-wire arrays of embodiment 1 gained, and Fig. 2 (b) is embodiment 1 gained Cu
2the low power electron scanning micrograph of S@ITO-3 nano-wire array.
Fig. 3 (a) is the high power electron scanning micrograph of three grades of ITO nano-wire arrays of embodiment 1 gained, and Fig. 3 (b) is embodiment 1 gained Cu
2the high power electron scanning micrograph of S@ITO-3 nano-wire array.
Fig. 4 is embodiment 1 gained Cu
2the high power transmission electron microscope photo of S ITO-3 nanometer linear array.
Fig. 5 is embodiment 1 gained Cu
2s@ITO-3 nano-wire array is used as quantum dot sensitized solar cell to the IV curve of electrode (Fig. 5 (a)) and IPCE curve (Fig. 5 (b)).
Embodiment
The experimental technique using in following embodiment if no special instructions, is conventional method.
In following embodiment, material used, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, parcel Cu
2the tertiary oxidation indium stannum nanowire array composite material (Cu of S shell
2s@ITO-3) and application
(1) prepare tertiary oxidation indium stannum nanowire array
By Metallic Indium Powder and glass putty according to mol ratio 10:1, in tube furnace, be heated to 800 ℃, then source region temperature is reacted after 20 minutes and is naturally cooled to room temperature at 800 ℃, be placed in advance position, crystallizing field in tube furnace (temperature is 400 ℃ of left and right) sputter on the FTO electro-conductive glass of Au particle (average grain diameter is 5 nanometers) can growth certain length ITO nano-wire array.
Select average length be 10 microns ITO nano-wire array (wherein, the diameter of nano wire is about 120 nanometers) as the matrix of load, adopt the method for similar golden auxiliary catalysis, by Metallic Indium Powder and glass putty according to mol ratio 10:1, in tube furnace, be heated to 800 ℃, then source region temperature is reacted after 15 minutes and is naturally cooled to room temperature at 800 ℃, being placed in advance on the ITO nano-wire array of position, crystallizing field in tube furnace (temperature is 400 ℃ of left and right) can growth 15 minutes, obtains the branch-like ITO nano-wire array secondary structure of certain length.
Select average length be 5 microns branch-like ITO nano-wire array (wherein, the diameter of nano wire branch is about 100 nanometers) as the matrix of load, adopt the method for similar golden auxiliary catalysis, by Metallic Indium Powder and glass putty according to mol ratio 10:1, in tube furnace, be heated to 800 ℃, then source region temperature is reacted after 10 minutes and is naturally cooled to room temperature at 800 ℃, being placed in advance in the branch-like ITO nano-wire array secondary structure of position, crystallizing field in tube furnace (temperature is 400 ℃ of left and right) can growth 10 minutes, (length of the ITO nano wire of the third level structure obtaining is about 1 micron to obtain the branch-like ITO nano-wire array tertiary structure of certain length, diameter is about 80 nanometers).
(2) utilize ion-exchange coated Cu on tertiary oxidation indium stannum nanowire array
2s shell
This branch-like ITO nano-wire array tertiary structure is placed in the aqueous solution of 22mL cadmium sulfate (15mM), temperature is elevated to after 65 ℃, add 28mL ammoniacal liquor (being diluted in 150mL water) and 22mL thiocarbamide (0.75mM), keep 65 ℃ of reactions 11 minutes; Transfer to subsequently containing in the aqueous solution of 0.5M stannous chloride of 10mL, at 50 ℃, react 30 minutes.Then with natural drying after washed with de-ionized water sample, finally under Ar atmosphere, 300 ℃ of calcining samples 30 minutes, in branch-like ITO nano-wire array tertiary structure, evenly wrapped up the Cu that thickness is about 30 to 60 nanometers
2s shell, is Cu
2s@ITO-3.
Fig. 1 is the present embodiment gained Cu
2s@ITO nano-wire array and three grades of ITO nano-wire arrays and In
2o
3the powder x-ray diffraction spectrogram of standard P DF card, as known in the figure, can prepare Cu according to the method described above
2s@ITO-3 composite material.
Fig. 2 (a) is the low power electron scanning micrograph of three grades of ITO nano-wire arrays of the present embodiment gained, as seen from the figure, can prepare according to the method described above three grades of ITO nano-wire arrays.
Fig. 2 (b) is the present embodiment gained Cu
2the low power electron scanning micrograph of S@ITO-3 nano-wire array, as seen from the figure, Cu
2s shell evenly and is densely grown on the surface of ITO nano-wire array.
Fig. 3 (a) is the high power electron scanning micrograph of three grades of ITO nano-wire arrays of the present embodiment gained, as seen from the figure, can prepare according to the method described above three grades of ITO nano-wire arrays.
Fig. 3 (b) is the present embodiment gained Cu
2the high power electron scanning micrograph of S@ITO-3 nano-wire array, as seen from the figure, Cu
2s shell evenly and is densely grown on the surface of ITO nano-wire array, Cu
2the thickness of S shell is 30 to 60 nanometers.
Fig. 4 is the present embodiment gained Cu
2the high power transmission electron microscope photo of S@ITO-3 nano wire, as seen from the figure, Cu
2s shell crystallinity is fine, simultaneously Cu
2interface between S and ITO is very good, and lattice line connects together in interface, and this epitaxially grown structure obtaining is conducive to transmission and the collection of electronics.
By above-mentioned evaluation collection of illustrative plates, further confirmed, method of the present invention can obtain tertiary oxidation indium stannum nanowire coated outside and Cu
2nano-wire array material (the Cu of S shell
2s@ITO-3).
The Cu that uses the present embodiment to prepare
2tri-grades of nano-wire array materials of S@ITO-3, as to electrode, are used cadmium sulfide and the cadmium selenide titanium dioxide porous membrane of sensitization altogether, use 1M vulcanized sodium (Na
2s) and many sulphur electrolyte of preparing of 1M sulphur (S), prepare quantum dot sensitized solar cell device.Adopt the 450W Model91150 of Newport company type instrument test IV curve, adopt the IQE-200 of Newport company test system and test IPCE curve.In test process, adopt metal copper sheet to control incident light area and be prepared as 0.16cm
2, radiation parameter is solar irradiation condition (100mW/cm of standard
2).
As shown in Figure 5, be this enforcement gained Cu
2s@ITO-3 nano-wire array is used as quantum dot sensitized solar cell to the IV curve of electrode (Fig. 5 (a)) and IPCE curve (Fig. 5 (b)), can learn, the photoelectric conversion efficiency of the solar cell that this is quantum dot sensitized is 6.12%, monochromatic light conversion efficiency is the highest at 505nm place, reaches 73.6%.
Embodiment 2, parcel Cu
2the stair oxidation indium stannum nanowire array composite material (Cu of S shell
2s@ITO-1) and application
Basic identical in concrete preparation method and embodiment 1, difference is: adopt a CVD legal system as the matrix of load, finally to prepare Cu for one-level ITO nano-wire array (wherein, the diameter of nano wire is about 100 nanometers)
2s@ITO-1.
The Cu preparing through the present embodiment
2s@ITO-1, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 5.31%.
Embodiment 3, parcel Cu
2the secondary oxidation indium stannum nanowire array composite material (Cu of S shell
2s@ITO-2) and application
Basic identical in concrete preparation method and embodiment 1, difference is: adopt twice CVD legal system as the matrix of load, finally to prepare Cu for secondary ITO nano-wire array (wherein, the diameter of nano wire is about 100 nanometers)
2s@ITO-2 (diameter of the ITO nano wire of the second level structure obtaining is 100 nanometers).
The Cu preparing through the present embodiment
2s@ITO-2, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 5.62%.
Embodiment 4, parcel Cu
2the level Four tin indium oxide nano-wire array composite material (Cu of S shell
2s@ITO-4) and application
Basic identical in concrete preparation method and embodiment 1, difference is: adopt four CVD legal systems as the matrix of load, finally to prepare Cu for level Four ITO nano-wire array (wherein, the diameter of nano wire is about 100 nanometers)
2s@ITO-4 (obtain three, the length of the ITO nano wire of quaternary structure is 1 micron, diameter is 80 nanometers).
The Cu preparing through the present embodiment
2s@ITO-4, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 5.76%.
Embodiment 5, SILAR method parcel Cu
2the tertiary oxidation indium stannum nanowire array composite material (SILAR-Cu of S shell
2s@ITO-3) and application
Basic identical in concrete preparation method and embodiment 1, difference is: by described multi-stage oxidizing indium stannum nanowire array continuous dip in stannous chloride and sodium sulfide solution, adopt continuous ionic layer absorption method to prepare three grades of ITO nano-wire arrays (wherein, the diameter of third level nano wire is about 80 nanometers) as the matrix of load, under the reaction condition of 20 ℃, continuous adsorption is 10 times, each 1 minute time, finally prepare SILAR-Cu
2s@ITO-3 (the ITO@Cu of the third level structure obtaining
2the length of S nano wire is 1 micron, and diameter is 160 nanometers).
The SILAR-Cu preparing through the present embodiment
2s@ITO-3, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 3.85%.
Embodiment 6, magnetron sputtering method parcel Cu
2the tertiary oxidation indium stannum nanowire array composite material (PVD-Cu of S shell
2s@ITO-3) and application
Basic identical in concrete preparation method and embodiment 1, difference is: employing magnetron sputtering method (radio frequency sputtering), target material is Cu
2s, power is 150 watts, and sputtering pressure is 3 millitorrs, and the time is 1000 seconds, prepares three grades of ITO nano-wire arrays (wherein, the diameter of third level nano wire is about 80 nanometers) and, as the matrix of load, finally prepares PVD-Cu
2s@ITO-3 (the ITO@Cu of the third level structure obtaining
2the length of S nano wire is 1 micron, and diameter is 120 nanometers).
The Cu preparing through the present embodiment
2s@ITO-3, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 2.55%.
Embodiment 7, the parcel Cu based on FTO substrate
2the tertiary oxidation indium stannum nanowire array composite material (FTO-Cu of S shell
2s@ITO-3) and application
Basic identical in concrete preparation method and embodiment 1, difference is: selection FTO electro-conductive glass, as conductive substrates, finally prepares FTO-Cu
2s@ITO-3.
The FTO-Cu preparing through the present embodiment
2s@ITO-3, as to electrode, according to the solar cell device of method assembling quantum dot sensitization in the same manner as in Example 1, and tests its photoelectric conversion performance, and its photoelectric conversion efficiency is respectively 4.94%.
The Cu of embodiment 8, embodiment 1 preparation
2s ITO-3 as the quantum dot sensitized solar cell of dyestuff to electrode
Use the Cu preparing in embodiment 1
2s@ITO-3 nano-wire array, as to electrode, is used the titanium dioxide porous membrane of dyestuff N719 sensitization as light anode, uses 0.6M PMII, 0.1M guanidine thiocyanate (C
2h
6n
4s), 0.03M iodine (I
2), 0.5M tert .-butylpyridine using acetonitrile and valeronitrile by volume the mixed solvent of 17:3 as electrolyte, prepare the quantum dot sensitized solar cell device of dyestuff.
After tested, the photoelectric conversion efficiency of the quantum dot sensitized solar cell of above-mentioned dyestuff is 5.50%.
Comparative example 1,
According to embodiment 1 in essentially identical method, Direct precipitation Cu on FTO electro-conductive glass
2s nano particle, then, as to electrode material, prepares quantum dot sensitization solar battery according to method in the same manner as in Example 1, and it is 3.23% that test obtains photoelectric conversion efficiency.
Comparative example 2,
According to embodiment 1 in essentially identical method, at three grades of ITO nano-wire array outer cladding Cu
2after S, without calcining is direct, as to electrode material, according to the method identical with embodiment 1, prepare quantum dot sensitization solar battery, it is 4.15% that test obtains photoelectric conversion efficiency.
It should be noted that, above-described embodiment is just used for illustrating technical characterictic of the present invention, is not used for limiting patent claim of the present invention.Such as the reactant relating in the present embodiment, also can use other reactant, the length of three grades of ITO nano-wire arrays that adopt in embodiment also can adopt the ITO nano-wire array of other progression.But its principle still belongs to patent protection category of the present invention.
Claims (10)
1. a multi-stage oxidizing indium stannum nanowire array composite material, it comprises the multi-stage oxidizing indium stannum nanowire array being grown in conductive substrates, on described multi-stage oxidizing indium stannum nanowire array, is enclosed with cuprous sulfide shell.
2. composite material according to claim 1, is characterized in that: the progression of described multi-stage oxidizing indium stannum nanowire array is 1～5 grade;
In described multi-stage oxidizing indium stannum nanowire array, the length of every grade of tin indium oxide nano-wire is 1 micron～30 microns, and diameter is 50 nanometer～300 nanometers.
3. composite material according to claim 1 and 2, is characterized in that: the thickness of described cuprous sulfide shell is 5 nanometer～100 nanometers;
Described conductive substrates is indium oxide tin glass or fluorine-doped tin oxide glass.
4. the preparation method of composite material described in any one in claim 1～3, comprises the steps:
(1) take gold nano grain as catalyst, by chemical vapour deposition technique, in described conductive substrates, press progression deposition growing tin indium oxide nano-wire successively, obtain described multi-stage oxidizing indium stannum nanowire array;
(2) by following 1)-3) in method coated Cu on described multi-stage oxidizing indium stannum nanowire array described in any
2s shell:
1) by chemical bath deposition method, coated CdS shell on described multi-stage oxidizing indium stannum nanowire array; Then by ion-exchange, described CdS shell is changed into Cu
2s shell;
2) by continuous ionic layer absorption method, coated Cu on described multi-stage oxidizing indium stannum nanowire array
2s shell;
3) by magnetron sputtering method, coated Cu on described multi-stage oxidizing indium stannum nanowire array
2s shell;
(3) under inert atmosphere, through calcining and obtain described composite material.
5. preparation method according to claim 4, is characterized in that: in step (1), the particle diameter of described gold nano grain is 2～10 nanometers;
The described multi-stage oxidizing indium stannum nanowire array indium source used of growing is indium metal and/or indium oxide;
The described multi-stage oxidizing indium stannum nanowire array Xi Yuan used that grows is metallic tin and/or tin oxide;
The mol ratio of described indium source and described Xi Yuan is 1～30:1.
6. according to the preparation method described in claim 4 or 5, it is characterized in that: in step (1), growth described tin indium oxide nano-wire array He Xi source, indium source used is heated into gaseous state under the condition of 600～1000 ℃, and be 5～120 minutes heating time;
The growth course of described multi-stage oxidizing indium stannum nanowire array is carried out in crystallizing field, and the temperature of described crystallizing field is 300～550 ℃, and growth time is 5～120 minutes.
7. according to the preparation method described in any one in claim 4-6, it is characterized in that: step (2) 1),
The cadmium salt that described chemical bath deposition method is used in cadmium acetate, caddy, cadmium sulfate and cadmium nitrate at least one;
The sulfosalt that described chemical bath deposition method is used in sulphur powder, thiocarbamide, thiosemicarbazides and thioacetamide at least one;
The temperature of described chemical bath deposition method is 0～100 ℃, and the time is 0.1～8 hour;
Described ion-exchange comprises the steps:
The multi-stage oxidizing indium stannum nanowire array of the coated CdS shell obtaining is transferred in the aqueous solution of mantoquita, through ion-exchange reactions, is about to described CdS shell and changes into Cu
2s shell;
Described mantoquita is at least one in cuprous acetate, stannous chloride and cuprous sulfate;
The temperature of described ion-exchange reactions is 5～90 ℃, and the time is 0.5～60 minute.
8. according to the preparation method described in any one in claim 4-6, it is characterized in that: step (2) 2),
Described continuous ionic layer absorption method comprises the steps:
Described multi-stage oxidizing indium stannum nanowire array continuous dip, in mantoquita and the sulfosalt aqueous solution, through the absorption of continuous ionic layer, is coated to Cu on described multi-stage oxidizing indium stannum nanowire array
2s shell;
Described mantoquita is at least one in cuprous acetate, stannous chloride and cuprous sulfate;
Described sulfosalt is at least one in vulcanized sodium, potassium sulfide and ammonium sulfide;
The temperature of described continuous ionic layer absorption method is 5～50 ℃, and continuous adsorption number of times is 1～20 time, and the time of each absorption is 0.5～5 minute.
9. according to the preparation method described in any one in claim 4-6, it is characterized in that: step (2) 3),
Described magnetron sputtering method adopts radio frequency sputtering method;
The condition of described radio frequency sputtering method is as follows:
Power is 100～300 watts, and sputtering pressure is 3～10 millitorrs, and the time is 200～2000 seconds.
In claim 1-3 described in any one multi-stage oxidizing indium stannum nanowire array composite material as solar cell to the application in electrode.
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Application publication date: 20141112 |