CN103602982A - Non-vacuum preparation method of light absorption layer of copper indium gallium sulfur selenium (CIGSSe) thin film solar cell - Google Patents
Non-vacuum preparation method of light absorption layer of copper indium gallium sulfur selenium (CIGSSe) thin film solar cell Download PDFInfo
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Abstract
The invention relates to a non-vacuum preparation method of a light absorption layer of a copper indium gallium sulfur selenium (CIGSSe) thin film solar cell. The method comprises the following steps: according to the stoichiometric ratio of Cu to In to Ga in CuxInyGa(1-y)SzSe(2-z), dissolving a copper-containing compound, an indium-containing compound and a gallium-containing compound in an organic alcohol solution containing a complexing agent and a sulfur-containing micromolecule reagent, adding a certain viscosity modifier and solution modifier and forming a clear, transparent and stable organic precursor solution, wherein the x is greater than or equal to 0.6 and less than or equal to 1, the y is greater than or equal to 0 and less than or equal to 1, the z is greater than or equal to 0 and less than or equal to 2, the copper-containing compound is at least one of copper oxide, cuprous oxide, copper hydroxide and copper acetylacetonate, the indium-containing compound is at least one of indium oxide, indium hydroxide and indium acetylacetonate and the gallium-containing compound is at least one of gallium oxide, gallium hydroxide and gallium acetylacetonate; depositing a precursor thin film on a conducting layer of a substrate by using the organic precursor solution; and annealing the precursor thin film in the atmosphere of chalcogen to form the light absorption layer.
Description
Technical field
The present invention relates generally to the preparation method of copper indium gallium sulphur selenium (CIGSSe) thin film solar cell light absorption layer.Belong to solar cell energy field.
Background technology
Energy environment is closely bound up with the survival and development of human society, is accompanied by the process of economic globalization, and energy environment issues becomes whole world facing and problem demanding prompt solution.Development and utilization clean, renewable energy source is the only way which must be passed that solves energy environment issues.Sun power is a kind of renewable energy source that cleans, enriches, is not subject to regional limits, and inexhaustible, and the effective exploitation of visible sun power and utilization have very important strategic importance.Solar cell is human use's sun power one of the most effective form.Copper indium gallium sulphur selenium film solar battery is the solar cell that obtains high conversion efficiency in thin film solar cell of new generation, and the flexible substrate copper-indium-galliun-selenium CIGS solar-energy photo-voltaic cell of Swiss Confederation's Materials science and the research and development of technology experiment chamber has reached 20.4% high conversion efficiency and refreshed world record.It has many-sided advantage that cost is low, efficiency is high, the life-span is long, band gap is adjustable, low light level performance is good, capability of resistance to radiation is strong, and the potentiality of Mirae Corp. are very huge.
In the making method of optical absorption layer of copper indium gallium sulphur selenium film solar battery, what obtain higher conversion efficiency is some evaporating deposition techniques, as composite film, magnetron sputtering, molecular beam epitaxy etc., but the vacuum apparatus that these class methods are used is very expensive, raw material availability is low, production efficiency is also low, and prepares in enormous quantities solar cell because device-restrictive is difficult to big area, and the method is restricted in Mirae Corp.ization application.Therefore,, in order to reduce thin-film solar cells production cost, the method for antivacuum Liquid preparation methods light absorbing zone film has received everybody concern gradually.
Antivacuum liquid phase preparation process mainly contains two kinds, and the first, for synthetic nanocrystalline being distributed in designated solvent formed to slurry, forms precursor thin film by antivacuum liquid phase filming technology, then forms copper indium gallium sulphur selenium film through annealing.But the control condition of nanocrystalline size and size distribution is very strict, stoichiometric ratio is difficult to regulation and control, and the long carbochain organism of surface adsorption is difficult to remove, slurry free settling, and the nanocrystalline preparation in enormous quantities of high quality is still a huge challenge, makes the method complex process, repeatable poor.
The second is clear solution method, and adopting anhydrous hydrazine is a wherein famous class as solvent.The method is dissolved in diazanyl solvent by the chalcogenide of copper, indium, gallium and sulphur, selenium simple substance, forms the source solution of stable copper, indium, gallium, sulphur, selenium, by antivacuum liquid phase filming technology, forms precursor thin film, then forms copper indium gallium sulphur selenium film through annealing.But anhydrous hydrazine has severe corrosive and explosivity, must under protective atmosphere, operate, cause complex technical process and danger, limit its application in scale operation.Meanwhile, liquid phase method based on alcoholic solution obtains extensive concern, the method is often used metal halide salt or acetate as source metal, easy residual impurity halogen family ion in film while using halide salt, causes negative impact to device, in addition, first the method deposits and obtains amorphous oxides precursor thin film, make to need in annealing process with hydrogen reducing, this can waste a lot of time and the energy, and the use of explosion gas also makes technological process more dangerous.Binding agent often joins in alcoholic solution continuous in cracking film with regulator solution viscosity preparation, but carbon residue easily appears in adding of binding agent in film, and the carbon in film suppresses the growth of crystal grain, leaves one deck amorphous enriched carbon layer.After introducing sulphur source in solution the solution-stabilized time shorter, be prone to precipitation, and obtain solution process can be used the steps such as heating, vacuum, not only complex process and very consuming time.
Can find out, antivacuum liquid phase method also has many defects and deficiency in preparing optical absorption layer of copper indium gallium sulphur selenium film solar battery.Invent a kind of novel preparation method and overcome the shortcoming of above existence, will more be conducive to the propelling of copper indium gallium sulphur selenium film solar battery industrialization.
Summary of the invention
For solving the problems such as the solution preparation existing in antivacuum Liquid preparation methods optical absorption layer of copper indium gallium sulphur selenium film solar battery is complicated, impurity is residual, the object of the present invention is to provide a kind of novel alcoholic solution to prepare the method for optical absorption layer of copper indium gallium sulphur selenium film solar battery.
At this, the invention provides a kind of antivacuum preparation method of optical absorption layer of copper indium gallium sulphur selenium film solar battery, comprising:
(1) according to Cu
xin
yga
1-ys
zse
2-zmiddle Cu, In, the stoichiometric ratio of Ga, by copper-containing compound, containing indium compound, with be dissolved in the Organic Alcohol solution that contains complexing agent and sulfur-bearing small molecules reagent containing gallium compound, and add certain viscosity modifier and solution conditioning agent, form clear and stable organosilane precursor liquid solution, 0.6≤x≤1 wherein, 0≤y≤1, 0≤z≤2, described copper-containing compound is cupric oxide, Red copper oxide, at least one in copper hydroxide and acetylacetone copper, described is Indium sesquioxide containing indium compound, at least one in indium hydroxide and Indium Tris acetylacetonate, described is gallium oxide containing gallium compound, at least one in gallium hydroxide and methyl ethyl diketone gallium,
(2) by described organosilane precursor liquid solution by antivacuum solution film-forming technique, deposition precursor film heating, drying on the conductive layer of substrate; And
(3) described precursor thin film is formed to optical absorption layer of copper indium gallium sulphur selenium film solar battery through annealing under sulfur family element atmosphere.
The present invention be take metal oxide, metal hydroxides and/or acetylacetonate as source metal, can be in film residual impurity ion.Do not need to prepare each provenance solution and mixed again, and only need a step can prepare precursor solution, so solution preparation process is simple and consuming time few, and can accurately control stoichiometric ratio again.And, owing to adding complexing agent, viscosity modifier, solution conditioning agent etc., make precursor solution clear and stable, thereby preparation process all can operate in air, and the film forming is evenly distributed, good quality.In addition, method technique of the present invention is simple, equipment and raw materials cost low, be easy to realize scale operation.
Preferably, 0.6≤y≤1,0<z≤1.5.
Preferably, in described organosilane precursor liquid solution, the concentration of Cu is 0.05～0.3mol/L.
Preferably, in described organosilane precursor liquid solution, the mol ratio of Cu, S, complexing agent is 1:(5～80): (2～20).
Preferably, in described organosilane precursor liquid solution, the concentration of described viscosity modifier is 0～0.05g/mL.
Preferably, described complexing agent is one or more the mixture in quadrol, butylamine, hexylamine, thanomin, diethanolamine, trolamine, ammoniacal liquor, ammonia, α-amino isopropyl alcohol and triethylamine.
Preferably, described sulfur-bearing small molecules reagent is one or more the mixture in thiocarbamide, thioacetamide, thioacetic acid, Thiovanic acid, thiohydracrylic acid and dithiocarbonic anhydride.
Preferably, described Organic Alcohol is one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol, Virahol and propyl carbinol.
Preferably, described viscosity modifier is one or more the mixture in ethylene glycol, propylene glycol, glycerol, polyvinylpyrrolidone, ethyl cellulose, the saturating alcohol of turps, triton x-100, polyoxyethylene glycol-200, polyoxyethylene glycol-300, PEG-4000 and polyoxyethylene glycol-600.
Preferably, described solution conditioning agent is: (a) sulfur family element, comprises one or more in sulphur, selenium and tellurium; (b) alkali metal compound, comprises alkali metal hydroxide and/or halogenide; And/or (c) alkaline earth metal compound, comprise alkaline earth metal oxide, oxyhydroxide and/or halogenide.
Preferably, in described step (2), described antivacuum solution film-forming technique is spin-coating method, crystal pulling method, silk screen print method, spray pyrolysis or the operation skill in using a kitchen knife in cookery.
Preferably, in described step (2), described substrate is sheet glass, ceramic plate, stainless steel plate or plastic plate.
Preferably, in described step (2), the temperature of described heating, drying is 150～400 ℃, is preferably 200～400 ℃.
Preferably, in described step (3), the temperature of described annealing is 300～650 ℃, is preferably 400～600 ℃; Annealing time is 20～90 minutes, is preferably 30～60 minutes.
Preferably, in described step (3), described sulfur family element atmosphere comprises one or more in sulphur simple substance, hydrogen sulfide, selenium simple substance and Selenium hydride.
Preferably, the thickness of described optical absorption layer of copper indium gallium sulphur selenium film solar battery is 500～2500nm, is preferably 800～2000nm.
Advantage of the present invention comprises: (1) solution preparation process is simple and consuming time few, and (2) solution is stable in the air, and preparation process all can operate in air, and (3) equipment and raw materials cost are low, (4) inclusion-free ion residues, and (5) stoichiometric ratio is controlled.
Accompanying drawing explanation
Fig. 1 is scanning electronic microscope (SEM) figure of the prepared CIGSSe thin film solar cell light absorption layer of embodiment 1;
Fig. 2 is the I-V curve of the prepared CIGSSe thin film solar cell of embodiment 1.
Embodiment
Below in conjunction with accompanying drawing and following embodiment, further illustrate the present invention, should be understood that accompanying drawing and following embodiment are only for the present invention is described, and unrestricted the present invention.
The invention provides a kind of novel alcoholic solution and prepare the method for optical absorption layer of copper indium gallium sulphur selenium film solar battery, particularly, as example, can adopt following steps.
First, according to Cu
xin
yga
1-ys
zse
2-z(0.6≤x≤1,0≤y≤1,0≤z≤2) stoichiometric ratio of copper, indium, gallium in, by copper-containing compound, be dissolved in the Organic Alcohol solution that contains complexing agent and sulfur-bearing small molecules reagent containing indium compound with containing gallium compound, add if desired certain viscosity modifier and/or solution conditioning agent, to form clear and stable organosilane precursor liquid solution.At Cu
xin
yga
1-ys
zse
2-zin, 0.6≤x≤1; 0≤y≤1, is preferably 0.6≤y≤1; 0≤z≤2, are preferably 0<z≤1.5.
Wherein, copper-containing compound can be one or more of cupric oxide, Red copper oxide, copper hydroxide or acetylacetone copper; Containing indium compound, can be one or more of Indium sesquioxide, indium hydroxide or Indium Tris acetylacetonate; Containing gallium compound, can be one or more of gallium oxide, gallium hydroxide or methyl ethyl diketone gallium.
In described organosilane precursor liquid solution, the concentration of Cu can be 0.05～0.3mol/L.
Complexing agent and sulfur-bearing small molecules reagent can be 1:(5～80 by the mol ratio of Cu, S, complexing agent): (2～20) carry out dosage.
Complexing agent includes but not limited to one or more the mixture in quadrol, butylamine, hexylamine, thanomin, diethanolamine, trolamine, ammoniacal liquor, ammonia, α-amino isopropyl alcohol and triethylamine.
Sulfur-bearing small molecules reagent includes but not limited to one or more the mixture in thiocarbamide, thioacetamide, thioacetic acid, Thiovanic acid, thiohydracrylic acid and dithiocarbonic anhydride.
Organic Alcohol includes but not limited to one or more the mixture in methyl alcohol, ethanol, n-propyl alcohol, Virahol and propyl carbinol.
If desired, in order to make organosilane precursor liquid solution obtain suitable viscosity and surface tension, can add viscosity modifier and/or solution conditioning agent, its add-on is for making organosilane precursor liquid solution clear and stable, for example the add-on of viscosity modifier can be 0～0.05g/mL, but should be understood that if precursor solution viscosity and surface tension are suitable, can not add viscosity modifier and/or solution conditioning agent.
Viscosity modifier includes but not limited to one or more the mixture in ethylene glycol, propylene glycol, glycerol, polyvinylpyrrolidone, ethyl cellulose, the saturating alcohol of turps, triton x-100, polyoxyethylene glycol-200, polyoxyethylene glycol-300, PEG-4000 and polyoxyethylene glycol-600.
Solution conditioning agent includes but not limited to: (a) sulfur family element, comprises one or more in sulphur, selenium and tellurium; (b) alkali metal compound, comprises alkali metal hydroxide and/or halogenide; And/or (c) alkaline earth metal compound, comprise alkaline earth metal oxide, oxyhydroxide and/or halogenide.
Secondly, by the organosilane precursor liquid solution of preparation by antivacuum solution film-forming technique, deposition precursor film heating, drying (for example on hot-plate, drying) on the conductive layer of substrate.
Wherein, antivacuum solution film-forming technique includes but not limited to spin-coating method, crystal pulling method, silk screen print method, spray pyrolysis or the operation skill in using a kitchen knife in cookery.
Substrate for example can adopt sheet glass, ceramic plate, stainless steel plate or plastic plate.Conductive layer can adopt the conductive layer that thin film solar cell is conventional, for example molybdenum layer.
Can be heated to 150～400 ℃, preferably dry for 200～400 ℃.
Finally, the precursor thin film of preparation is formed to CIGSSe thin film solar cell light absorption layer through annealing under sulfur family element atmosphere.
Wherein, the atmosphere of the preferred sulfur-bearing of sulfur family element atmosphere and/or selenium, includes but not limited to one or more in sulphur simple substance, hydrogen sulfide, selenium simple substance and Selenium hydride.
Annealing temperature can be 300～650 ℃, is preferably 400～600 ℃.Annealing time can be 20～90 minutes, is preferably 30～60 minutes.
The chemical constitution of the CIGSSe thin film solar cell light absorption layer forming is Cu
xin
yga
1-ys
zse
2-z(0.6≤x≤1,0≤y≤1,0≤z≤2).Its thickness can be 500～2500nm, is preferably 800～2000nm.Inclusion-free ion residues in this CIGSSe thin film solar cell light absorption layer.Fig. 1 illustrates scanning electronic microscope (SEM) figure of the CIGSSe thin film solar cell light absorption layer of an example of the present invention, and known referring to Fig. 1, this absorption layer is evenly distributed, good quality.
Formed after CIGSSe thin film solar cell light absorption layer, can also continue on its basis to prepare thin film solar cell.Preparation method can adopt the preparation method of known thin film solar cell, for example can adopt on the surface of this CIGSSe film chemical bath method deposition Cadmium Sulfide (CdS) film, adopt again magnetron sputtering method to prepare native oxide zinc (i-ZnO) layer and Al-Doped ZnO (ZnO:Al) layer, thereby make CIGSSe thin film solar cell.Fig. 2 illustrates the I-V curve that utilizes the prepared CIGSSe thin film solar cell of the CIGSSe thin film solar cell light absorption layer of an example of the present invention, and the open circuit voltage of this battery is 0.611V, and short-circuit current is 24.88mA/cm
2, packing factor is 56.59%, photoelectric efficiency can reach 8.6%.
The present invention be take metal oxide, metal hydroxides and/or acetylacetonate as source metal, can be in film residual impurity ion.Do not need again to prepare each provenance solution and mixed again, and only need a step can prepare precursor solution, so solution preparation process is simple and consuming time few, and can accurately control stoichiometric ratio.And, owing to adding complexing agent, viscosity modifier, solution conditioning agent etc., make precursor solution clear and stable, thereby preparation process all can operate in air, and the film forming is evenly distributed, good quality.In addition, method technique of the present invention is simple, easy to operate, with low cost, and facility investment is low, and raw material availability is high, can big area prepare, and is easy to realize scale operation.
As from the foregoing, the present invention has the following advantages: (1) solution preparation process is simple and consuming time few, and (2) solution is stable in the air, preparation process all can operate in air, (3) equipment and raw materials cost are low, (4) inclusion-free ion residues, and (5) stoichiometric ratio is controlled.
Further exemplify embodiment below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The quality that following example is concrete, volume, temperature, time etc. are only also examples in OK range, and those skilled in the art can be done in suitable scope and be selected by explanation herein, and do not really want to be defined in the below concrete numerical value of example.
Embodiment 1
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.7in
0.7ga
0.3s
0.2se
1.8the stoichiometric ratio of middle copper, indium, gallium, by 0.35mmol Red copper oxide (Cu
2o), 0.7mmol indium hydroxide (In (OH)
3), 0.3mmol gallium hydroxide (Ga (OH)
3) be dissolved in the mixed organic solvents of 10mL Virahol, thioacetic acid, ethylene glycol, thanomin, wherein the volume ratio of Virahol, thioacetic acid, ethylene glycol, thanomin is 5:2:2:1, and stirring at room obtains the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by spin-coating method, is prepared to CIGSSe precursor thin film and 300 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in selenium atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1000nm target Cu
0.7in
0.7ga
0.3s
0.2se
1.8compound film.
The surface of prepared film adopts chemical bath method deposition Cadmium Sulfide (CdS) film, and thickness is 60nm, and magnetron sputtering method is prepared native oxide zinc (i-ZnO) layer and Al-Doped ZnO (ZnO:Al) layer, and thickness is respectively 100nm and 600nm, makes Cu
0.7in
0.7ga
0.3s
0.3se
0.7base thin film solar battery, its photoelectric efficiency can reach 8.6%.
Embodiment 2
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
1.0in
0.7ga
0.3s
0.6se
1.4the stoichiometric ratio of middle copper, indium, gallium, by 1.0mmol cupric oxide (CuO), 0.7mmol indium hydroxide (In (OH)
3), 0.3mmol acetylacetonate gallium (Ga (C
5h
7o
2)
3) be dissolved in the mixed organic solvents of 10mL methyl alcohol, thioacetic acid, diethanolamine, wherein the volume ratio of methyl alcohol, thioacetic acid, diethanolamine is 7:2:1, stirring at room obtains the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by spin-coating method, is prepared to CIGSSe precursor thin film and 300 ℃ of oven dry on hot-plate at the bottom of the stainless steel lining of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in sulphur and selenium atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1200nm target Cu
0.8in
0.7ga
0.3s
0.6se
1.4compound film.
Embodiment 3
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.8in
0.8ga
0.2s
0.6se
1.4the stoichiometric ratio of middle copper, indium, gallium, by 0.4mmol Red copper oxide (Cu
2o), 0.8mmol indium hydroxide (In (OH)
3), 0.2mmol acetylacetonate gallium (Ga (C
5h
7o
2)
3) be dissolved in the mixed organic solvents of 10mL ethanol, thioacetic acid, quadrol, glycerol, wherein the volume ratio of ethanol, thioacetic acid, quadrol, glycerol is 6.8:2:1:0.2, and stirring at room obtains the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by crystal pulling method, is prepared to CIGSSe precursor thin film and 300 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in hydrogen sulfide and selenium atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1000nm target Cu
0.8in
0.8ga
0.2s
0.6se
1.4compound film.
Embodiment 4
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.8in
1.0s
0.6se
1.4the stoichiometric ratio of middle copper, indium, by 0.8mmol copper hydroxide (Cu (OH)
2), 0.8mmol indium hydroxide (In (OH)
3), be dissolved in the mixed organic solvents of 10mL ethanol, dithiocarbonic anhydride, hexylamine, wherein the volume ratio of ethanol, dithiocarbonic anhydride, hexylamine is 8:1:1, and add a small amount of polyvinylpyrrolidone, stirring at room to obtain the organosilane precursor liquid solution of clear, stable cupric, indium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by crystal pulling method, is prepared to CIGSSe precursor thin film and 400 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in sulphur and selenium atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1000nm target Cu
0.8in
1.0s
0.6se
1.4compound film.
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.75in
0.6ga
0.4s
0.6se
1.4the stoichiometric ratio of middle copper, indium, gallium, by 0.75mmol cupric oxide (CuO), 0.6mmol acetylacetonate indium (In (C
5h
7o
2)
3), 0.4mmol acetylacetonate gallium (Ga (C
5h
7o
2)
3) be dissolved in the mixed organic solvents of 10mL Virahol, thioacetic acid, ammoniacal liquor, propylene glycol, wherein the volume ratio of Virahol, thioacetic acid, ammoniacal liquor, propylene glycol is 4:2:1:3, and add a small amount of sodium hydroxide (NaOH), stirring at room to obtain the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by spin-coating method, is prepared to CIGSSe precursor thin film and 350 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in hydrogen sulfide and selenium atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1200nm target Cu
0.75in
0.6ga
0.4s
0.6se
1.4compound film.
Embodiment 6
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.75in
0.7ga
0.3s
2the stoichiometric ratio of middle copper, indium, gallium, by 0.75mmol copper hydroxide (Cu (OH)
2), 0.8mmol acetylacetonate indium (In (C
5h
7o
2)
3), 0.2mmol acetylacetonate gallium (Ga (C
5h
7o
2)
3), 4mmol thioacetamide is dissolved in the mixed organic solvents of 10mL n-propyl alcohol, butylamine, the saturating alcohol of turps, wherein the volume ratio of n-propyl alcohol, butylamine, the saturating alcohol of turps is 6:1:3, and add a small amount of lithium fluoride (LiF), stir the organosilane precursor liquid solution that obtains clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by the operation skill in using a kitchen knife in cookery, is prepared to CIGSSe precursor thin film and 300 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in sulphur atmosphere 530 ℃ annealing 40 minutes, generating thickness is 1500nm target Cu
0.75in
0.7ga
0.3s
2compound film.
Embodiment 7
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.7in
0.7ga
0.3s
0.3se
1.7the stoichiometric ratio of middle copper, indium, gallium, by 0.7mmol copper hydroxide (Cu (OH)
2), 0.7mmol indium hydroxide (In (OH)
3), 0.3mmol gallium hydroxide (Ga (OH)
3) be dissolved in 10mL Virahol, thiacetic mixed organic solvents, wherein Virahol, thiacetic volume ratio are 4:1, and add a certain amount of ethyl cellulose, pass into enough ammonias, stirring at room obtains the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by silk screen print method, is prepared to CIGSSe precursor thin film and 350 ℃ of oven dry on hot-plate in the glass substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in hydrogen sulfide and selenium atmosphere 550 ℃ annealing 30 minutes, generating thickness is 1600nm target Cu
0.7in
0.7ga
0.3s
0.3se
1.7compound film.
Embodiment 8
The preparation of organosilane precursor liquid solution: press Cu in light absorbing zone
0.9in
0.9ga
0.1s
0.4se
1.6the stoichiometric ratio of middle copper, indium, gallium, by 0.45mmol Red copper oxide (Cu
2o), 0.9mmol indium hydroxide (In (OH)
3), 0.1mmol acetylacetonate gallium (Ga (C
5h
7o
2)
3) be dissolved in the mixed organic solvents of 10mL Virahol, thioacetic acid, trolamine, wherein the volume ratio of Virahol, thioacetic acid, trolamine is 7:2:1, and stirring at room obtains the organosilane precursor liquid solution of clear, stable cupric, indium, gallium, sulphur;
The preparation of CIGSSe precursor thin film: organosilane precursor liquid solution, by spin-coating method, is prepared to CIGSSe precursor thin film and 350 ℃ of oven dry on hot-plate on the titanium foil substrate of plating molybdenum;
The anneal of CIGSSe film: by precursor thin film in hydrogen sulfide and Selenium hydride atmosphere 500 ℃ annealing 30 minutes, generating thickness is 1000nm target Cu
0.9in
0.9ga
0.1s
0.4se
1.6compound film.
Industrial applicability: the antivacuum preparation method of optical absorption layer of copper indium gallium sulphur selenium film solar battery of the present invention, technique is simple, easy to operate, with low cost, facility investment is low, and raw material availability is high, can big area prepare, be easy to realize scale operation, can be applied to the preparation field of thin film solar cell.
Claims (12)
1. an antivacuum preparation method for optical absorption layer of copper indium gallium sulphur selenium film solar battery, is characterized in that, comprising:
(1) according to Cu
xin
yga
1-ys
zse
2-zmiddle Cu, In, the stoichiometric ratio of Ga, by copper-containing compound, containing indium compound, with be dissolved in the Organic Alcohol solution that contains complexing agent and sulfur-bearing small molecules reagent containing gallium compound, and add certain viscosity modifier and solution conditioning agent, form clear and stable organosilane precursor liquid solution, 0.6≤x≤1 wherein, 0≤y≤1, 0≤z≤2, described copper-containing compound is cupric oxide, Red copper oxide, at least one in copper hydroxide and acetylacetone copper, described is Indium sesquioxide containing indium compound, at least one in indium hydroxide and Indium Tris acetylacetonate, described is gallium oxide containing gallium compound, at least one in gallium hydroxide and methyl ethyl diketone gallium,
(2) by described organosilane precursor liquid solution by antivacuum solution film-forming technique, deposition precursor film heating, drying on the conductive layer of substrate; And
(3) described precursor thin film is formed to optical absorption layer of copper indium gallium sulphur selenium film solar battery through annealing under sulfur family element atmosphere.
2. preparation method according to claim 1, is characterized in that, 0.6≤y≤1,0<z≤1.5.
3. preparation method according to claim 1 and 2, is characterized in that, in described organosilane precursor liquid solution, the concentration of Cu is 0.05～0.3mol/L.
4. according to the preparation method described in any one in claims 1 to 3, it is characterized in that, in described organosilane precursor liquid solution, the mol ratio of Cu, S, complexing agent is 1:(5～80): (2～20).
5. according to the preparation method described in any one in claim 1 to 4, it is characterized in that, in described organosilane precursor liquid solution, the concentration of described viscosity modifier is 0～0.05g/mL.
6. according to the preparation method described in any one in claim 1 to 5, it is characterized in that, described complexing agent is at least one in quadrol, butylamine, hexylamine, thanomin, diethanolamine, trolamine, ammoniacal liquor, ammonia, α-amino isopropyl alcohol and triethylamine.
7. according to the preparation method described in any one in claim 1 to 6, it is characterized in that, described sulfur-bearing small molecules reagent is at least one in thiocarbamide, thioacetamide, thioacetic acid, Thiovanic acid, thiohydracrylic acid and dithiocarbonic anhydride.
8. according to the preparation method described in any one in claim 1 to 7, it is characterized in that, described Organic Alcohol is at least one in methyl alcohol, ethanol, n-propyl alcohol, Virahol and propyl carbinol.
9. according to the preparation method described in any one in claim 1 to 8, it is characterized in that, described viscosity modifier is at least one in ethylene glycol, propylene glycol, glycerol, polyvinylpyrrolidone, ethyl cellulose, the saturating alcohol of turps, triton x-100, polyoxyethylene glycol-200, polyoxyethylene glycol-300, PEG-4000 and polyoxyethylene glycol-600.
10. according to the preparation method described in any one in claim 1 to 9, it is characterized in that, described solution conditioning agent is:
(a) sulfur family element, comprises sulphur, selenium and/or tellurium;
(b) alkali metal compound, comprises alkali metal hydroxide and/or alkali metal halide; And/or
(c) alkaline earth metal compound, comprises alkaline earth metal oxide, alkaline earth metal hydroxides and/or alkaline earth metal halide.
11. according to the preparation method described in any one in claim 1 to 10, it is characterized in that, in described step (2), described antivacuum solution film-forming technique is spin-coating method, crystal pulling method, silk screen print method, spray pyrolysis or the operation skill in using a kitchen knife in cookery;
Described substrate is sheet glass, ceramic plate, stainless steel plate or plastic plate;
The temperature of described heating, drying is 150～400 ℃.
12. according to the preparation method described in any one in claim 1 to 11, it is characterized in that, in described step (3), the temperature of described annealing is 300～650 ℃, and annealing time is 20～90 minutes;
Described sulfur family element atmosphere comprises at least one in sulphur simple substance, hydrogen sulfide, selenium simple substance and Selenium hydride.
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| CN106340545A (en) * | 2016-09-14 | 2017-01-18 | 南京邮电大学 | Manufacturing of CIS and CIGS thin-film solar cell light absorption layer and application of new solvent during manufacturing |
| CN106460143A (en) * | 2014-06-17 | 2017-02-22 | 纽升股份有限公司 | Selenization or sufurization method of roll to roll metal substrates |
| CN109678123A (en) * | 2018-11-30 | 2019-04-26 | 中国科学院物理研究所 | Copper zinc tin sulfur selenium thin-film solar cells and its precursor solution preparation method |
| CN109817734A (en) * | 2018-12-26 | 2019-05-28 | 北京铂阳顶荣光伏科技有限公司 | A kind of preparation method of copper-indium-galliun-selenium film solar cell absorbed layer |
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