CN102569508B - Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell - Google Patents
Thin-film solar photovoltaic cell with nano wire array structure and preparation method for thin-film solar photovoltaic cell Download PDFInfo
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Photovoltaic Devices (AREA)
Abstract
The invention discloses a method for preparing a thin-film solar photovoltaic cell with a copper indium gallium selenide (CIGS) nano wire array structure. The method comprises the following steps of: growing a large-area cuprous sulfide or copper sulfide nano wire array by adopting a gas-solid reaction method, and converting the cuprous sulfide or copper sulfide nano wire array into a CIGS nano wire array by physical vapor deposition and heat treatment methods. The component, the phase structure and the energy band structure of the semiconductor nano wire array can be regulated by controlling the categories of deposition elements, the deposition sequence, the deposition process, post treatment and the like, so that solar photovoltaic cells with different structures and properties are prepared. Through the cell, light reflection is reduced, light absorption is increased, the probability of producing current carriers can be increased, the probability of recombination of holes and electrons is reduced, and the photoelectric conversion efficiency is greatly improved. The method is low in cost, the preparation processes are controllable, the prepared nano wire array is uniform in structure distribution, and preparation of the nano structural thin-film solar photovoltaic cell with large area and high photoelectric conversion efficiency can be realized.
Description
Technical field
The invention belongs to solar-energy photo-voltaic cell technical field, particularly a kind of CIGS nanowire array structure thin film solar photovoltaic cell and preparation method thereof.
Background technology
Along with the continuous increase of the mankind to energy demand, the non-renewable energy resources such as coal, oil, natural gas all will face short crisis.In addition, also there is the shortcoming of self in these energy, and they easily cause environmental pollution, causes the problems such as acid rain, greenhouse effect, makes the mankind's survival and development face threat, and the development and utilization of new and renewable sources of energy is also just imperative.
Solar cell can directly be changed solar energy and electric energy, is problem comparatively concerned in development and utilization solar energy.Its application can change existing energy starved present situation, and contributes to reduce the problem of environmental pollution that the above-mentioned energy causes.
Current, studying more solar cell has the types such as monocrystalline silicon, polysilicon, amorphous silicon, GaAs, cadmium sulfide, cadmium tellurium, copper indium sulphur, Copper Indium Gallium Selenide, Cu-In-Ga-Se-S.Requirement photoelectric conversion efficiency of the solar battery being improved along with people and the development of nanometer technology, more people have started the research of thin film solar cell to being made up of above-mentioned material, nano wire solar cell, nanometer rods solar cell etc.
Copper Indium Gallium Selenide (CIGS) photovoltaic cell is current important film photovoltaic cell.CIGS is direct gap semiconductor, there is the higher absorption coefficient of light, electricity conversion is higher, and the photoelectric conversion efficiency of CIGS thin film solar cell prepared by the laboratory scale of current report has reached 20%, but still has larger gap apart from theoretical transformation efficiency.
Publication number is the preparation method of the disclosed optical absorption layer of copper indium gallium sulphur selenium film solar battery of Chinese patent application of CN101471394, adopt antivacuum liquid chemical method to prepare CIGSS film, this preparation method's technique is simple, with low cost, equipment investment is few, raw material availability is high, and controllability is strong, is easy to realize preparation and the large-scale production of large area film.
Publication number is the preparation method of the disclosed flexible CIGS thin-film solar cell of the Chinese patent application of CN 101459200A and absorbed layer thereof, select flexible metal or polyimide film to do substrate, after magnetron sputtering Mo film, prepare again metal preformed layer, after vacuum seal, putting into stove heats up, solid-state selenium source region temperature is controlled at 180-300 degree Celsius, carries out selenization, makes metal preformed layer change semiconductive thin film into.This technical process controllable repeatability, has reduced the consumption of selenium or sulphur, and process is controlled, and equipment is simple.
Publication number is the method that the disclosed magnetron sputtering method of the Chinese patent application of CN 101768729A is prepared light absorption layer of copper-indium-gallium-selenium film solar cell, adopt and on hearth electrode, pass through magnetron sputtering method, adopt single target sputter, rich copper target and poor copper target while or successively sputter, prepare and there is high reaction activity, CIGS precursor thin film that can fast reaction sintering, then CIGS precursor thin film is heat-treated, fast reaction generates the CIGS solar cell light absorption layer film smooth, fine and close, even, photoelectric properties are good.The method controllability is strong, and film quality is high, good uniformity, and technique is simple, is applicable to suitability for industrialized production.
It is high that above-mentioned several method can be prepared quality; the CIGS film of good uniformity; but CIGS thin film solar photovoltaic cell conversion efficiency prepared by large-scale production is generally no more than 15%; CIGS thin film solar cell 20% photoelectric conversion efficiency of preparing lower than laboratory, also well below theoretical transformation efficiency.
The CIGS solar-energy photo-voltaic cell of nanowire array structure is the emphasis of various countries' research and development at present.Nano-wire array photovoltaic cell has advantages of that film photovoltaic cell does not possess, and main advantage has: the one, and nano-wire array can effectively reduce light reflection, increases the absorbability of photovoltaic cell to light; The 2nd, can make full use of nano-wire array diameter less, the absorption of light occurs in the axial of nano-wire array, distance between nano-wire array is less than optical wavelength and increases the absorption to light, and the crystal lattice preferred orientation of nano wire reduced lattice distortion, reduces reflection of light; The 3rd, the specific area of nano-wire array is large, has increased the probability that charge carrier produces, and transporting of charge carrier occur in radially, has reduced the probability of hole and electron recombination, can realize the significantly raising of solar-energy photo-voltaic cell photoelectric conversion efficiency.So groups of people attempt adopting distinct methods to prepare CIGS nano-wire array solar-energy photo-voltaic cell light absorbing zone.
The people such as Carmelo Sunseria are by the CIGS nano-wire array that uses the constant voltage deposition process of alumina formwork to prepare, the atomic percent of Ga and other three kinds of elements has reached 2.4, optical band gap has reached the people such as 1.55.Yi Cui and has utilized for the first time the VLS growing method of Au particulate catalytic, prepares CIGS nano wire.But above method is all not suitable for preparing large area CIGS nano-wire array photovoltaic cell, limited to the control ability of its lattice structure and orientation, also do not prepare can be practical nano thread structure film photovoltaic cell.In nanostructure CIGS film photovoltaic cell preparation process, also there is not a kind of comparatively perfect production method of preparing nano-wire array solar-energy photo-voltaic cell.Ubiquitous subject matter be difficult to realize large area manufacture, preparation cost is higher, and each element ratio and the more difficult control of material microstructure.
Summary of the invention
In order to solve the deficiency existing in the existing technology of preparing of above-mentioned nano-wire array photovoltaic cell, primary and foremost purpose of the present invention is to provide a kind of preparation method of nano wire CIGS film photovoltaic cell, it is simple that the method has technique, cost is lower, can carry out large area processing, to not advantages of higher of equipment requirement.
The nano wire CIGS film photovoltaic cell that provides a kind of said method to prepare is provided another object of the present invention.
Object of the present invention is achieved through the following technical solutions: the preparation method of a kind of Copper Indium Gallium Selenide (CIGS) nanowire array structure thin film solar photovoltaic cell, on the basis of the method by the cuprous sulfide (Cu2S) prepared in gas-solid reaction method or copper sulfide (CuS) nano-wire array, prepare Copper Indium Gallium Selenide (CIGS) nanowire array structure thin film solar photovoltaic cell in conjunction with physical gas-phase deposite method and heat treatment method.
Said method specifically comprises following operating procedure:
(1) on the substrate after cleaning, by physical vaporous deposition or electrochemical deposition method, deposit successively dorsum electrode layer and copper film, obtained depositing the substrate of copper film;
(2) substrate that step (1) gained has been deposited to copper film is put into reaction vessel, pass into after the oxygen of setting and the mist of hydrogen sulfide, control reaction temperature, by gas-solid reaction, copper film is converted to cuprous sulfide or copper sulphide nano linear array; The cuprous sulfide preparing or copper sulphide nano linear array are put into aqueous hydrochloric acid solution dissolves away surface oxide layer, pass through again physical vaporous deposition, the film that deposition contains N kind element in cuprous sulfide or copper sulphide nano linear array, obtains p-type conductor nano tube/linear array absorbed layer; Described N is natural number, and span is 2≤N≤9;
(3) step (2) gained sample is put into heating furnace, under the protection of Ar gas, H
2se or H
2in S atmosphere, carry out selenizing or sulfuration, temperature is controlled between 300 DEG C～600 DEG C, and the time is 0.1～3h, until form the p-type semiconductor CIGS nano-wire array of required phase structure and composition;
(4), at the p-type semiconductor CIGS nano-wire array surface deposition N-shaped semiconductor lamella obtaining, obtain having the core/shell type nano-wire array of p-n junction after step (3) is processed;
(5) have on the core/shell type nano-wire array of p-n junction at step (4) gained, deposit successively Window layer and metal grate electrode by physical vaporous deposition, metal alloyization forms metal ohmic contact, obtains copper-indium-gallium-selenium nanowire array structural membrane solar-energy photo-voltaic cell.
The described physical vaporous deposition of step (1) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or selenizing method; Described electrochemical deposition method is coating by pulse electrochemical deposition, constant voltage electrochemical deposition or Constant Electric Current chemical deposition; Described substrate is pottery, mica, high molecule plastic, metal, silicon chip, glass or stainless steel substrates; Described back electrode is molybdenum (Mo), aluminium (Al), gold (Au), copper (Cu), ito glass (ITO), silver (Ag), tungsten (W), nickel (Ni) or titanium (Ti), and the thickness of described dorsum electrode layer is 50nm～50 μ m.
In the described mist of step (2), the ratio of hydrogen sulfide and oxygen is 1: 100～1: 0; Described reaction temperature is controlled at 10～200 DEG C; The described gas-solid reaction time is 1～500h; The concentration of described aqueous hydrochloric acid solution is 0.001～2mol/L.
The described p-type conductor nano tube/linear array of step (2) absorbed layer is by semiconducting alloy (Cu
xb
1-x) C
y(D
zs
1-z)
2composition, wherein 0 < x≤1,0≤y≤1,0≤z < 1, B is more than one in silver and gold, and C is more than one in aluminium, indium and gallium, and D is more than one in selenium and tellurium; Described physical vaporous deposition is sputtering method, thermal evaporation, electron-beam vapor deposition method or laser beam evaporation method.Described thermal evaporation is first coevaporation indium-gallium, then evaporates copper, then coevaporation indium-gallium; Or first evaporate gallium-selenium, then evaporate indium-selenium, finally evaporate copper; Or first evaporate indium-selenium, then evaporate gallium-selenium, finally evaporate copper-selenium; Or first coevaporation indium-gallium-selenium coevaporation copper, selenium again; The target adopting in described sputtering method is the target being made up of more than one elements in copper, indium, gallium and selenium.
Nanowire diameter in the described p-type semiconductor of step (3) CIGS nano-wire array is 10nm～500nm, and length is 100nm～500 μ m.
The method of the described deposition N-shaped of step (4) semiconductor lamella is chemical bath, spin coating, infiltration, electrochemical deposition or physical vapour deposition (PVD); Described N-shaped semiconductor lamella is cadmium sulfide (CdS), zinc sulphide (ZnS), zinc selenide (ZnSe), magnesium oxide (MgO), zinc oxide (ZnO), indium selenide (In
2se
3), indium sulfide (In
2s
3), indium zinc selenium (InZnSe
3), tin oxide (SnO
2) or artificial gold (SnS
2); The thickness of described N-shaped semiconductor lamella is 1nm～200nm.
The described physical vaporous deposition of step (5) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or selenizing method; The thickness of described Window layer is 1nm～10 μ m, and described Window layer is doping zinc-oxide, ito thin film, graphene film or carbon nano-tube film; Described metal grate electrode is molybdenum (Mo), aluminium (Al), gold (Au), copper (Cu), tungsten-titanium alloy, ito glass (ITO), silver (Ag, tungsten (W), nickel (Ni) or titanium (Ti).
A copper-indium-gallium-selenium nanowire array structural membrane solar-energy photo-voltaic cell of preparing according to said method, this battery is by core/shell type nano-wire array, Window layer and the metal grate electrode of substrate, back electrode, p-n junction.
The present invention applies the most ripe industrial physical gas phase deposition technology at present, on the basis of cuprous sulfide or copper sulphide nano linear array, prepares solar-energy photo-voltaic cell.Preparation technology is simple, and cost is lower, not high to equipment requirement, can carry out easily large-area applications, and the electricity conversion of the nano-structured solar photovoltaic cell of preparation is higher.
Compared with prior art, tool has the following advantages and effect in the present invention:
The present invention adopts physical gas phase deposition technology to prepare solar-energy photo-voltaic cell on the basis of cuprous sulfide or copper sulphide nano linear array, and preparation cost is lower.The absorbed layer nano-wire array of preparation is evenly distributed, and because cuprous sulfide or copper sulphide nano linear array can be carried out large area deposition on different substrates simultaneously, so can carry out on this basis the preparation of large-area nano structural membrane solar-energy photo-voltaic cell.Meanwhile, on the basis in cuprous sulfide or copper sulphide nano linear array, then the method for dopant deposition element, can change the composition of nano-wire array, thereby prepare the nano-structured solar photovoltaic cell of different component.This nano-structured solar photovoltaic cell has used nano-wire array diameter less, and the absorption of light occurs in the axial of nano-wire array, and the distance between nano-wire array is less than optical wavelength and increases the absorption to light; Use the preferred orientation of nano-wire array to reduce lattice distortion, reduce reflection of light; Use the large feature of specific area of nano-wire array, increase the probability that charge carrier produces, and transporting of charge carrier occur in radially, reduced the probability of hole and electron recombination, realized the significantly raising of solar-energy photo-voltaic cell photoelectric conversion efficiency.
Brief description of the drawings
Fig. 1 is solar-energy photo-voltaic cell structural representation of the present invention, and wherein 1 is substrate, and 2 is back electrode, and 3 is p-type conductor nano tube/linear array, and 4 is N-shaped semiconductor lamella, and 5 is Window layer, and 6 is metal gates.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
This example is selected CuInS
2as the composition of conductor nano tube/linear array, CdS is as N-shaped layer, infiltrate the means as deposition cadmium sulfide layer, Al-Doped ZnO layer is as Window layer, thermal evaporation is as the means of deposition In, Al-Doped ZnO layer, metal grate electrode, back electrode, copper film, back electrode is selected Mo, and metal grate electrode is selected Ti, and substrate is selected glass.
Concrete steps are as follows:
(1) after the NaOH solution of 1mol/L and the hydrochloric acid solution of 1mol/L clean respectively, then deposit the Mo layer that a layer thickness is 800nm on sheet glass substrate with absolute ethyl alcohol and deionized water successively ultrasonic cleaning;
(2) on the substrate after thermal evaporation deposition Mo, evaporate the copper film that a layer thickness is 10um;
(3) substrate that step (2) gained has been evaporated to copper film is put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2, and sulfuration 18h, growth cuprous sulfide nano-wire array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of cuprous sulfide nano-wire array puts into 1mol/L dissolves surface oxide layer;
(5) will be placed in substrate frame through step (4) sample after treatment, thermal evaporation In, layer is absorbed after heat treatment;
(6) after evaporation finishes, carry out the infiltration of cadmium sulfide layer, first in the cadmium sulfate of 50mM, infiltrate 20s, with after deionized water rinsing, then infiltrate 20s in the vulcanized sodium of 50mM, then use deionized water rinsing, infiltrate successively multiple circulations, obtain the cadmium sulfide layer that thickness is 60nm;
(7) on the sample after infiltration, deposit Al-Doped ZnO layer, deposit thickness is 500nm; Finally evaporate a Ti fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make CIS nano-structured solar photovoltaic cell, as shown in Figure 1.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, and in P type layer prepared by the method, cuprous sulfide is mono-crystalline structures, deposit again In, less to reflection of light than polycrystalline and amorphous solar cell, find that through its p-type layer is tested its absorbance in whole visible region has all reached more than 1.5, than the p-type layer structure of film, its absorbance has increased nearly 70%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 2
This example is selected Cu (In, Ga) (S, Se)
2as the composition of conductor nano tube/linear array, CdS is as N-shaped layer, Al-Doped ZnO layer is as Window layer, spin coating is as the means of deposition cadmium sulfide layer, magnetron sputtering is as the means of deposition In, Ga, Se, Al-Doped ZnO layer, metal grate electrode, back electrode and copper film, back electrode is selected Al, and metal grate electrode is selected Cu, and substrate is selected silicon chip.
Concrete steps are as follows:
(1) after the hydrochloric acid solution that closes 1mol/L through the NaOH solution of 1mol/L cleans, then deposit one deck Al in silicon chip substrate with absolute ethyl alcohol and deionized water successively ultrasonic cleaning, the thickness of Al is 800nm;
(2) on the substrate after magnetron sputtering deposition Al, sputter a layer thickness is about the copper film of 1um;
(3) by step (2) gained sputter the substrate of copper film put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2, sulfuration 14h, the sub-nano-array of growth sulfuration;
(4) step (3) gained the has been grown substrate of copper sulphide nano linear array, puts into 1mol/L aqueous hydrochloric acid solution surface oxide layer is dissolved;
(5) will be placed on magnetic control sputtering device rotary substrate frame through step (4) sample after treatment, cosputtering In, Ga and Se, layer is absorbed after heat treatment;
(6) after sputter finishes, 50mM cadmium nitrate is dropped on sample after spin coating, then the vulcanized sodium of 50mM is dropped in to spin coating on sample, repeat successively multiple circulations, the thickness that finally deposits cadmium sulfide shell is 60nm;
(7) on the sample after spin coating, evaporate Al-Doped ZnO layer, deposit thickness is 500nm; A last sputter Cu fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make Cu-In-Ga-Se-S nano-structured solar photovoltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in P type layer prepared by the method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.4, than the p-type layer structure of plane, its absorbance has increased nearly 60%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 3
This example is selected Cu (In
0.7, Ga
0.3) (Se, S)
2as the composition of conductor nano tube/linear array, ZnS is as N-shaped layer, and Al-Doped ZnO layer is as Window layer, and chemical bath is as the means of deposition ZnS.Electron beam evaporation is as the means of deposition In, Ga, Se, Al-Doped ZnO layer, metal grate electrode, back electrode and copper film, and back electrode is selected W, and metal grate electrode is selected Ni, and substrate is selected mica.
Concrete steps are as follows:
(1) on the mica sheet substrate of newly cutting open, deposit one deck W, the thickness of W is 800nm;
(2), on the substrate after electron beam evaporation W, evaporation a layer thickness is about the copper film of 1um;
(3) substrate that step (2) gained has been evaporated to copper film is put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2, and sulfuration 12h, growth copper sulphide nano linear array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of copper sulphide nano linear array puts into 1mol/L dissolves surface oxide layer;
(5) will be placed on rotary substrate frame through step (4) sample after treatment, layered evaporator In, Ga, Se, layer is absorbed after heat treatment;
(6) after evaporation finishes, by sample, at zinc sulfate, thiocarbamide, carries out chemical bath in the mixed solution of ammoniacal liquor and hydrazine hydrate, deposition zinc sulphide shell, and thickness is 60nm;
(7) sample after chemical bath is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 500nm, finally deposits a Ni fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make Cu-In-Ga-Se-S nano-structured solar photovoltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in P type layer prepared by the method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 4
This example is selected Cu (In
0.8, Ga
0.2) (Se
0.8, S
0.2)
2as the composition of conductor nano tube/linear array, ZnS is as N-shaped layer, and Al-Doped ZnO layer is as Window layer, and chemical bath is as the means of deposition ZnS.Selenizing method is as the means of deposition In, Ga, Se, and electron beam evaporation is as the means of deposition In, Ga, Se, Al-Doped ZnO layer, metal grate electrode, back electrode, copper film, and back electrode is selected Ni, and metal grate electrode is selected Cu, and substrate is selected stainless steel substrates.
Concrete steps are as follows:
(1) on the stainless steel substrates substrate through absolute ethyl alcohol and deionized water successively ultrasonic cleaning, deposit layer of Ni, the thickness of Ni is 800nm;
(2) on the substrate after electron beam evaporation Ni, evaporate the copper film that a layer thickness is about 5um;
(3) substrate that step (2) gained has been evaporated to copper film is put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2, and sulfuration 12h, growth cuprous sulfide nano-array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of cuprous sulfide nano-wire array puts into 1mol/L dissolves surface oxide layer;
(5) sample of processing through step (4) is placed on rotary substrate frame, evaporation In, Ga element, then pass at high temperature selenizing of hydrogen selenide, layer is absorbed;
(6), after selenizing finishes, sample is carried out in the mixed solution of zinc sulfate, thiocarbamide, ammoniacal liquor and hydrazine hydrate to chemical bath, deposition zinc sulphide shell, thickness is 60nm;
(7) sample after chemical bath is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 500nm, finally deposits a Cu fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make Cu-In-Ga-Se-S nano-structured solar photovoltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in P type layer prepared by the method, cuprous sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.3, than the p-type layer structure of plane, its absorbance has increased nearly 50%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 5
This example is with Cu
2s is as the composition of conductor nano tube/linear array, CdS, ZnO are as N-shaped layer, Al-Doped ZnO layer is as Window layer, spin coating is as the means of depositing zinc oxide, chemical bath is as the means of deposition CdS, and sputter is as the means of deposition Al-Doped ZnO layer, metal grate electrode, back electrode, copper film, and back electrode is selected ITO, metal grate electrode is selected Mo, substrate Ceramics.
Concrete steps are as follows:
(1) after the NaOH solution of 1mol/L and the cleaning of the hydrochloric acid solution of 1mol/L, with sputter one deck ITO in the ceramic substrate of absolute ethyl alcohol and deionized water successively ultrasonic cleaning, the thickness of ITO is 700nm (also can directly select ito glass) again;
(2) on the substrate after sputtering sedimentation ITO, (also can directly select ito glass), the copper film that sputter a layer thickness is 1um;
(3) by step (2) gained sputter the substrate of copper film put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 4, sulfuration 18h, growth cuprous sulfide nano-wire array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of cuprous sulfide nano-wire array puts into 0.5mol/L dissolves surface oxide layer;
(5) will be placed in substrate frame through step (4) sample after treatment, sputter In, layer is absorbed after heat treatment;
(6) after sputter finishes,, carry out the infiltration of cadmium sulfide layer, first in the cadmium sulfate of 50mM, infiltrate 20s, with after deionized water rinsing, in the vulcanized sodium of 50mM, infiltrate 20s again, then use deionized water rinsing, infiltrate successively multiple circulations, obtain the cadmium sulfide layer that thickness is 60nm, carry out again the spin coating of zinc oxide film, 20g zinc nitrate is dissolved in 40mL absolute alcohol and adds monoethanolamine in 60 DEG C of water-baths, to carry out magnetic agitation 2.5h as stabilizer and prepare solution, and the quiet 72h of putting at room temperature., it is 3000r/min that sample pivoted frame rotating speed is set; Under pivoted frame low speed rotation, the colloidal sol after quiet putting is dropped on substrate, then under High Rotation Speed, carry out spin coating, and toast 5min in the oven of 150 DEG C, naturally cooling, repeat spin coating 7 times; Horse expense stove is put into the substrate of colloidal sol in surface, first temperature is elevated to 250 DEG C and processes 10min, then again temperature is elevated to 450 DEG C of annealing in process that continue 2h, obtain the zinc oxide film that thickness is 60nm;
(7) sample after spin coating is placed on to sputtering sedimentation Al-Doped ZnO layer in substrate frame, deposit thickness is 450nm, a last sputter W fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make cuprous sulfide nano-array solar-energy photo-voltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, and in P type layer prepared by the method, cuprous sulfide is mono-crystalline structures, deposit again In, less to reflection of light than polycrystalline and amorphous solar cell, find that through its p-type layer is tested its absorbance in whole visible region has all reached more than 1.5, than the p-type layer structure of film, its absorbance has increased nearly 70%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 6
This example is selected Cu (In, Ga) S
2as the composition of conductor nano tube/linear array, MgO is as N-shaped layer, and Al-Doped ZnO layer is as Window layer, and magnetron sputtering is as the means of deposition MgO.Electron beam evaporation is as the means of deposition In, Ga, Al-Doped ZnO layer, metal grate electrode, back electrode and copper film, and back electrode is selected Ag, and metal grate electrode is selected Cu, and substrate is selected polystyrene plastics.
Concrete steps are as follows:
(1) on the polystyrene plastics substrate through absolute ethyl alcohol and deionized water successively ultrasonic cleaning, evaporate one deck Ag, the thickness of Ag is 700nm;
(2) on the substrate after electron beam evaporation Ag, evaporate the copper film that a layer thickness is about 1um;
(3) substrate that step (2) gained has been evaporated to copper film is put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2.5, and sulfuration 12h, growth copper sulphide nano linear array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of copper sulphide nano linear array puts into 0.7mol/L dissolves surface oxide layer;
(5) will be placed on rotary substrate frame through step (4) sample after treatment, layered evaporator In, layer is absorbed after Ga heat treatment;
(6) after evaporation finishes, utilize magnesium oxide target, magnetron sputtering one deck magnesium oxide layer on the sample of preparing in (5), thickness is 70nm.
(7) sample after magnetron sputtering is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 600nm, finally deposits a Cu fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make copper indium gallium sulphur nano-structured solar photovoltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in P type layer prepared by the method, copper sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 7
This example is selected Cu (In
0.9ga
0.1) (Se
0.4s
0.6)
2as the composition of conductor nano tube/linear array, InSe is as N-shaped layer, and Al-Doped ZnO layer is as Window layer, and magnetron sputtering is as the method for deposition InSe.Electron beam evaporation is as the means of deposition In, Ga, Se, Al-Doped ZnO layer, metal grate electrode, back electrode and copper film, and back electrode is selected Ag, and metal grate electrode is selected Cu, and substrate is selected nickel sheet.
Concrete steps are as follows:
(1) on the nickel sheet through absolute ethyl alcohol and deionized water successively ultrasonic cleaning, evaporate one deck Ag, the thickness of Ag is 700nm;
(2) on the substrate after electron beam evaporation Ag, evaporate the copper film that a layer thickness is about 1um;
(3) substrate that step (2) gained has been evaporated to copper film is put into reactor, after the mist 10min that logical oxygen and hydrogen sulfide volume ratio are 1: 2.5, and sulfuration 12h, growth cuprous sulfide nano-wire array;
(4) step (3) gained the has been grown aqueous hydrochloric acid solution that the substrate of cuprous sulfide nano-wire array puts into 0.7mol/L dissolves surface oxide layer;
(5) will be placed on rotary substrate frame through step (4) sample after treatment, layered evaporator In, layer is absorbed after Ga, Se heat treatment;
(6) after evaporation finishes, utilize indium selenide target, magnetron sputtering one deck indium selenide layer on the sample of preparing in (5), thickness is 70nm;
(7) sample after magnetron sputtering is placed in substrate frame and evaporates Al-Doped ZnO layer, deposit thickness is 600nm, finally deposits a Cu fork formula electrode.
The sample of above-mentioned preparation is carried out forming ohmic contact after heating of metal alloying, make Cu-In-Ga-Se-S nano-structured solar photovoltaic cell.The specific area of this solar cell increases more with respect to other type solar cells, make the absorption area of light become large, simultaneously, in P type layer prepared by the method, cuprous sulfide is mono-crystalline structures, deposit again other element, less to reflection of light than polycrystalline and amorphous solar cell, through being tested, its p-type layer finds that its absorbance in whole visible region has all reached more than 1.2, than the p-type layer structure of plane, its absorbance has increased nearly 40%.In addition, the motion that the core/shell structure of this solar cell makes charge carrier radially, can reduce meeting of charge carrier, thereby improves nano-structured solar power conversion efficiency (pce).
Embodiment 8
The present embodiment except following characteristics other features with embodiment 8: described back electrode is Au, and described N-shaped shell is In2S, and N-shaped shell thickness is 1nm, and dorsum electrode layer thickness is 50nm, and the gas-solid reaction time is 1h, and watery hydrochloric acid concentration used is 0.001mol/L.
Embodiment 9
The present embodiment except following characteristics other features with embodiment 9: described metal grate electrode is Au, described N-shaped shell is InZnSe, Window layer is carbon nano-tube film, N-shaped shell thickness is 200nm, dorsum electrode layer thickness is 50um, the gas-solid reaction time is 500h, and used salt aqueous acid concentration is 5mol/L.
Embodiment 10
The present embodiment except following characteristics other features with embodiment 10: described N-shaped shell is SnO
2, Window layer is that graphene film, N-shaped shell thickness are 100nm, and dorsum electrode layer thickness is 25um, and the gas-solid reaction time is 30h, and used salt aqueous acid concentration is 3mol/L.
Embodiment 11
The present embodiment except following characteristics other features with embodiment 11: described metal grate electrode is that tungsten-titanium alloy, described N-shaped shell are SnS
2, Window layer is ito thin film, and N-shaped shell thickness is 80nm, and dorsum electrode layer thickness is 20um, and the gas-solid reaction time is 25h, used salt aqueous acid concentration is 2mol/L.
Above-described embodiment is preferably execution mode of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. the preparation method of a copper-indium-gallium-selenium nanowire array structural membrane solar-energy photo-voltaic cell, it is characterized in that: on the basis of the method by the cuprous sulfide prepared in gas-solid reaction method or copper sulphide nano linear array, prepare copper-indium-gallium-selenium nanowire array structural membrane solar-energy photo-voltaic cell in conjunction with physical gas-phase deposite method and heat treatment method;
The method specifically comprises following operating procedure:
(1) on the substrate after cleaning, by physical vaporous deposition or electrochemical deposition method, deposit successively dorsum electrode layer and copper film, obtained depositing the substrate of copper film;
(2) substrate that step (1) gained has been deposited to copper film is put into reaction vessel, pass into after the oxygen of setting and the mist of hydrogen sulfide, control reaction temperature, by gas-solid reaction, copper film is converted to cuprous sulfide or copper sulphide nano linear array; The cuprous sulfide preparing or copper sulphide nano linear array are put into aqueous hydrochloric acid solution dissolves away surface oxide layer, pass through again physical vaporous deposition, the film that deposition contains N kind element in cuprous sulfide or copper sulphide nano linear array, obtains p-type conductor nano tube/linear array absorbed layer; Described N is natural number, and span is 2≤N≤9;
(3) step (2) gained sample is put into heating furnace, under the protection of Ar gas, H
2se or H
2in S atmosphere, carry out selenizing or sulfuration, temperature is controlled between 300 DEG C～600 DEG C, and the time is 0.1～3h, until form the p-type semiconductor CIGS nano-wire array of required phase structure and composition;
(4), at the p-type semiconductor CIGS nano-wire array surface deposition N-shaped semiconductor lamella obtaining, obtain having the core/shell type nano-wire array of p-n junction after step (3) is processed;
(5) have on the core/shell type nano-wire array of p-n junction at step (4) gained, deposit successively Window layer and metal grate electrode by physical vaporous deposition, metal alloyization forms metal ohmic contact, obtains copper-indium-gallium-selenium nanowire array structural membrane solar-energy photo-voltaic cell.
2. preparation method according to claim 1, is characterized in that: the described physical vaporous deposition of step (1) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or selenizing method; Described electrochemical deposition method is coating by pulse electrochemical deposition, constant voltage electrochemical deposition or Constant Electric Current chemical deposition; Described substrate is pottery, mica, high molecule plastic, metal, silicon chip, glass or stainless steel substrates; Described back electrode is molybdenum, aluminium, gold, copper, ito glass, silver, tungsten, nickel or titanium, and the thickness of described dorsum electrode layer is 50nm～50 μ m.
3. preparation method according to claim 1, is characterized in that: in the described mist of step (2), the ratio of hydrogen sulfide and oxygen is 1:100～1:0; Described reaction temperature is controlled at 10～200 DEG C; The described gas-solid reaction time is 1～500h; The concentration of described aqueous hydrochloric acid solution is 0.001～2mol/L.
4. preparation method according to claim 1, is characterized in that: the described p-type conductor nano tube/linear array of step (2) absorbed layer is by semiconducting alloy (Cu
xb
1-x) C
y(D
zs
1-z)
2composition, wherein 0 < x≤1,0≤y≤1,0≤z < 1, B is more than one in silver and gold, and C is more than one in aluminium, indium and gallium, and D is more than one in selenium and tellurium; Described physical vaporous deposition is sputtering method, thermal evaporation, electron-beam vapor deposition method or laser beam evaporation method.
5. preparation method according to claim 4, is characterized in that: described thermal evaporation is first coevaporation indium-gallium, then evaporates copper, then coevaporation indium-gallium; Or first evaporate gallium-selenium, then evaporate indium-selenium, finally evaporate copper; Or first evaporate indium-selenium, then evaporate gallium-selenium, finally evaporate copper-selenium; Or first coevaporation indium-gallium-selenium coevaporation copper, selenium again; The target adopting in described sputtering method is the target being made up of more than one elements in copper, indium, gallium and selenium.
6. preparation method according to claim 1, is characterized in that: the nanowire diameter in the described p-type semiconductor of step (3) CIGS nano-wire array is 10nm～500nm, and length is 100nm～500 μ m.
7. preparation method according to claim 1, is characterized in that: the method for the described deposition N-shaped of step (4) semiconductor lamella is chemical bath, spin coating, infiltration, electrochemical deposition or physical vapour deposition (PVD); Described N-shaped semiconductor lamella is cadmium sulfide, zinc sulphide, zinc selenide, zinc oxide, indium selenide, indium sulfide, indium zinc selenium, tin oxide or artificial gold; The thickness of described N-shaped semiconductor lamella is 1nm～200nm.
8. preparation method according to claim 1, is characterized in that: the described physical vaporous deposition of step (5) is sputtering method, thermal evaporation, electron-beam vapor deposition method, laser beam evaporation method or selenizing method; The thickness of described Window layer is 1nm～10 μ m, and described Window layer is doping zinc-oxide, ito thin film, graphene film or carbon nano-tube film; Described metal grate electrode is molybdenum, aluminium, gold, copper, tungsten-titanium alloy, ITO glass, silver, tungsten, nickel or titanium.
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| CN103014624B (en) * | 2012-12-18 | 2015-01-07 | 合肥工业大学 | Preparation method of light-absorbing film of solar cell |
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| CN110071027B (en) * | 2019-04-24 | 2022-02-15 | 深圳先进技术研究院 | Field emission device for emitting X-rays and method for manufacturing the same |
| CN112331553B (en) * | 2019-07-16 | 2024-04-05 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nanowire monolithic epitaxy integrated structure, manufacturing method and application |
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