CN102251235A - Preparation method of Cu-Zn-Sn-S thin film - Google Patents
Preparation method of Cu-Zn-Sn-S thin film Download PDFInfo
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- CN102251235A CN102251235A CN2011101893912A CN201110189391A CN102251235A CN 102251235 A CN102251235 A CN 102251235A CN 2011101893912 A CN2011101893912 A CN 2011101893912A CN 201110189391 A CN201110189391 A CN 201110189391A CN 102251235 A CN102251235 A CN 102251235A
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Abstract
The invention discloses a preparation method of a Cu-Zn-Sn-S thin film, comprising the steps of: by adopting a successive ionic layer adsorption reaction method, sequentially or alternatively soaking one substrate in a cation precursor solution and an anion precursor solution to prepare a Cu2SnSx film and ZnS film laminated precast layer structure or a Cu2S film and ZnSnSx film laminated precast layer structure, and then performing heat treatment to obtain the Cu-Zn-Sn-S thin film; the cation precursor solution comprises at least one of copper ions, stannum ions and zinc ions, and the anion precursor solution is selected from at least one of a sodium sulfide solution, a potassium sulfide solution and an ammonium sulfide solution; the substrate is selected from one of glass, PI (polyimide), a stainless steel plate, a molybdenum plate and a titanium plate. The preparation method of Cu-Zn-Sn-S thin film not only solves the problem that the metal components are difficult to control, but also prevents the copper ions from moving to the surface of the film to form a sulfur copper phase. The preparation method is simple and applicable, low in cost and suitable for industrialization production.
Description
Technical field
The present invention relates to new copper zinc-tin-sulfur film solar cell absorption layer preparation methods, specifically be meant a kind of preparation method of copper-zinc-tin-sulfur film; Belong to the solar cell preparing technical field.
Background technology
In the middle of thin film solar cell material of new generation, has low cost, the copper-zinc-tin-sulfur (Cu of characteristics such as high-level efficiency and environmental friendliness
2ZnSnS
4) the thin film solar cell material become the emphasis and the focus of research.As solar cell absorption layer material, copper-zinc-tin-sulfur has suitable energy gap (1.5ev) and bigger photoabsorption coefficient (10
4Cm
-1More than), more crucial is this material component content on earth is abundant and safety non-toxic is pollution-free, so copper-zinc-tin-sulfur is considered to one of the most promising cheap photovoltaic material in the world.
The method that research at present prepares the copper-zinc-tin-sulfur film material has vacuum, antivacuum preparation method.Vacuum method has sputter, thermal evaporation, molecule epitaxial growth etc., and antivacuum method has galvanic deposit, spraying thermolysis, collosol and gel, coating method etc.With antivacuum method particularly chemical solution method prepare advantages such as copper-zinc-tin-sulfur film has equipment and technology is simple, and is with low cost with respect to vacuum method, be suitable for the large-area production of industrialization.But antivacuum method quality of forming film is generally not as vacuum production method, show that thin film composition is wayward, the film volumetric shrinkage causes crackle in the film drying annealing process, some organic additives are introduced the pollution effect battery efficiency of carbon, also have some deleterious additives to pollute the environment, increase the battery use cost.In addition no matter be that vacuum or antivacuum method prepare copper-zinc-tin-sulfur film, cupric ion migrates to film surface easily and forms sulphur copper phase and influence battery performance, and generally the sulphur copper phase that etching is removed the surface being carried out on the absorption layer surface with hypertoxic potassium cyanide, this has increased battery cost undoubtedly again.
Continuous ionic layer absorption reaction (SILAR) method is that the more a kind of chemical solution of Recent study prepares film process, this method is pollution-free, and preparation technology is simple, and is with low cost, and deposition substrate there is not particular requirement, be particularly suitable for industrial big area production.Present international and domestic investigator's great majority prepare binary metal sulfide such as ZnS with continuous ionic layer absorption reaction method, CdS and nano core-shell structure etc.For ternary metal sulfide such as CuInS
2, CuInSe
2The competing reaction absorption of metal ion when depositing because of the absorption reaction of continuous ionic layer Deng compound causes composition to control than difficult, so seldom report.As for quaternary metallic sulfide copper-zinc-tin-sulfur (Cu
2ZnSnS
4) report of continuous ionic layer absorption reaction also of no use preparation.The present invention proposes a kind ofly to prepare the method for copper-zinc-tin-sulfur film with the postheat treatment of continuous ionic layer absorption reaction deposition rhythmo structure, has both solved metal ingredient problem rambunctious, can stop cupric ion to cause forming sulphur copper phase to the film surface migration again.
Summary of the invention
The objective of the invention is to prepare the problem that copper-zinc-tin-sulfur film exists, propose a kind of method for preparing copper-zinc-tin-sulfur film with the postheat treatment of continuous ionic layer absorption reaction deposition rhythmo structure at present chemical solution method.
The preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, be adopt continuous ionic layer absorption reaction method with on the same substrate successively or alternately be immersed in positively charged ion precursor solution and the negatively charged ion precursor solution and prepare Cu
2SnS
xFilm and ZnS pellicular cascade preformed layer structure or Cu
2S film and ZnSnS
xPellicular cascade preformed layer structure is heat-treated then and is obtained copper-zinc-tin-sulfur film; Described alternately immersion, each soak time is 10～30 seconds, each back of soaking is with cleaning in the mobile deionized water 10～50 seconds; Contain at least a in copper, tin, the zine ion in the described positively charged ion precursor solution, described negatively charged ion precursor solution is selected from least a in sodium sulfide solution, potassium sulfide solution, the sulfuration ammonia solution; Described substrate is selected from a kind of in glass, PI, stainless steel substrates, molybdenum sheet, the titanium sheet.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, the copper in the described positively charged ion precursor solution, tin, zinc, sulfonium ion are obtained in deionized water solvent by the compound dissolution of cupric tin, zinc, sulphur; The described Cu of containing compound is selected from least a in the halogenide that contains Cu, nitrate, vitriol, the acetate; Described stanniferous compound is selected from least a in the halogenide that contains Sn, nitrate, the vitriol; Described zinciferous compound is selected from least a in the halogenide that contains Zn, nitrate, vitriol, the acetate; Vitriol, nitrate, the halogenide of preferred Cu; Preferred Zn halogenide, vitriol, acetate; The halogenide, the vitriol that preferably contain Sn.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, adopt continuous ionic layer absorption reaction method to prepare Cu
2SnS
xFilm and ZnSnS
xDuring film, contain complexing agent in the described positively charged ion precursor solution, described complexing agent is selected from least a in tartrate, sodium tartrate, citric acid, trolamine, ammonium fluoride, quadrol, the ammoniacal liquor, and the total mol concentration of described complexing agent is 0.1～1M/L.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, adopt continuous ionic layer absorption reaction legal system to be equipped with Cu
2SnS
xDuring film, cupric ion and tin ion volumetric molar concentration are respectively 0.001～0.2M/L and 0.001～0.2M/L in the described positively charged ion precursor solution; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, be equipped with Cu with continuous ionic layer absorption reaction legal system
2During the S film, described positively charged ion precursor solution cupric ion volumetric molar concentration is 0.001～0.2M/L, and adds suitable ammoniacal liquor, and wherein the ammoniacal liquor volumetric molar concentration is 0.1～5M/L; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, when being equipped with the ZnS film with continuous ionic layer absorption reaction legal system, described positively charged ion precursor solution zine ion volumetric molar concentration is 0.001～0.2M/L; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm;
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, be equipped with ZnSnS with continuous ionic layer absorption reaction legal system
xDuring film, zine ion and tin ion volumetric molar concentration are respectively 0.001～0.2M/L and 0.001～0.2M/L in the described positively charged ion precursor solution; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm;
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, the volumetric molar concentration of described negatively charged ion precursor solution is 0.05～0.2M/L.
Among the preparation method of a kind of copper-zinc-tin-sulfur film of the present invention, with the Cu of preparation
2SnS
xFilm and ZnS pellicular cascade or ZnSnS
xFilm and Cu2S pellicular cascade place under 200 ℃～600 ℃ sulfur-bearing atmosphere and annealed 5～60 minutes, obtain copper-zinc-tin-sulfur film; Described sulfur-bearing atmosphere is mixed evaporation selenium atmosphere, Ar+H for evaporation sulphur atmosphere, evaporation sulphur
2S atmosphere, N
2+ H
2At least a in the S atmosphere.
The present invention is owing to adopt above-mentioned processing method, the method for preparing copper-zinc-tin-sulfur film with the postheat treatment of continuous ionic layer absorption reaction deposition rhythmo structure, be easy to control thin film composition by regulating the ionic adsorption parameter on the one hand, use rhythmo structure to stop cupric ion to form sulphur copper phase on the other hand to surface transport, avoided the use of hypertoxic potassium cyanide and organic additive, and the film surface densification of preparing is smooth, can shrinkage cracking after the annealing, be suitable for preparing high efficiency absorbing layer of thin film solar cell material.The present invention can regulate each metallic element component proportions in the described copper-zinc-tin-sulfur film by metal ion volumetric molar concentration and cyclic deposition number of times in the change precursor solution; Sulfur vapor or hydrogen sulfide dividing potential drop when annealing by changing in the sulfur-bearing atmosphere are regulated sulphur content in the copper-zinc-tin-sulfur film.Both solved metal ingredient problem rambunctious, and can stop cupric ion to cause forming sulphur copper phase again to the film surface migration.Processing method method of the present invention is simply suitable, with low cost, is suitable for suitability for industrialized production.
Description of drawings
Accompanying drawing 1 is the Cu of the embodiment of the invention 1 preparation
2ZnSnS
4The XRD figure of film.
Accompanying drawing 2 is the Cu of the embodiment of the invention 1 preparation
2ZnSnS
4The sem photograph of film.Accompanying drawing 3 is
The Cu of the embodiment of the invention 1 preparation
2ZnSnS
4The Raman spectrogram of film.
Accompanying drawing 4 is the Cu of the embodiment of the invention 2 preparations
2ZnSnS
4The XRD figure of film.
Accompanying drawing 5 is the Cu of the embodiment of the invention 2 preparations
2ZnSnS
4The sem photograph of film.Accompanying drawing 6 is
The Cu of the embodiment of the invention 2 preparations
2ZnSnS
4The Raman spectrogram of film.
XRD and Raman analysis by accompanying drawing 1,3,4,6 learn that the embodiment of the invention 1,2 prepared samples are copper tin tin sulphur, do not have other dephasign, equate as sulphur copper.
The prepared copper-zinc-tin-sulfur sample thin film surface compact of the embodiment of the invention 1,2 is smooth as can be seen by the sem photograph of accompanying drawing 2,5, does not have slight crack.
Embodiment
Embodiment one
Step 1, preparation Cu
2SnS
xFilm:
1, positively charged ion precursor solution preparation: used medicine is an analytical reagent, adopts the deionized water preparation.Take by weighing a certain amount of CuSO
4, SnSO
4And tartrate, mix the beaker that the solution that is mixed with 100ml places 200ml, wherein CuSO
4, SnSO
4Be respectively 0.01M/L with tartaric volumetric molar concentration, 0.05M/L and 1.0M/L;
2, the preparation of negatively charged ion precursor solution: take by weighing a certain amount of Na
2The solution that S is mixed with 100ml places beaker, Na
2The volumetric molar concentration of S is 0.05M/L;
3, priority process dilute sulphuric acid, the slide glass that ammoniacal liquor and dehydrated alcohol cleaned immerses in the mixed-cation solution and carries out surface adsorption, and the time is 20 seconds, immerses in the mobile deionized water container to clean 20 seconds again, then immerses negatively charged ion presoma Na
2Reaction is 20 seconds in the S solution, at last slide glass is used mobile washed with de-ionized water 20 seconds, finishes a continuous ionic layer absorption reaction circulation;
4, repeat on slide glass, to obtain the Cu that thickness is about 500nm with cocycle 100 times
2SnS
xFilm.
Step 2, at Cu
2SnS
xThe lamination preformed layer structure that deposition ZnS film forms on the film:
1, positively charged ion precursor solution preparation: used medicine is an analytical reagent, adopts the deionized water preparation.Take by weighing a certain amount of ZnSO
4, the solution that is mixed with 100ml places the beaker of 200ml, wherein ZnSO
4Volumetric molar concentration is 0.05M/L.Add 25% ammoniacal liquor then, white precipitate at first appears in solution, continues to add ammoniacal liquor and obtains transparent positively charged ion precursor solution until sediment completely dissolve;
2, the preparation of negatively charged ion precursor solution: take by weighing a certain amount of Na
2The solution that S is mixed with 100ml places beaker, Na
2The volumetric molar concentration of S is 0.05M/L;
3, depositing Cu
2SnS
xThe slide glass of film immerses ZnSO
4Carry out surface adsorption in the cationic solution, the time is 20 seconds, immerses in the mobile deionized water container to clean 20 seconds again, then immerses negatively charged ion presoma Na
2Reaction is 20 seconds in the S solution, uses the mobile washed with de-ionized water at last 20 seconds, finishes a continuous ionic layer absorption reaction circulation;
4, repeat with cocycle 100 times, at Cu
2SnS
xDeposit thickness on the film and be about the ZnS film of 300nm.
Step 3, thermal treatment:
Depositing Cu
2SnS
xThe slide glass of film and ZnS film preformed layer structure places argon gas and hydrogen sulfide (95%Ar+5%H
2S) the following 500 ℃ of heating of mixed atmosphere are 30 minutes, obtain copper-zinc-tin-sulfur film (Cu on slide glass
2ZnSnS
4).After testing, each composition of gained copper-zinc-tin-sulfur film meets stoichiometric ratio, film energy gap E
g=1.5eV, uptake factor are 10
5Cm
-1, resistivity is 5.1 Ω cm, carrier concentration is 7.3 * 10
18Cm
-3, the XRD of film, scanning electron microscope and Raman spectrum shown in accompanying drawing 1～3, are learnt by XRD and Raman analysis that respectively prepared sample is a copper tin tin sulphur, does not have other dephasign, equate as sulphur copper.
Embodiment two
Step 1, preparation Cu
2The S film:
1, positively charged ion precursor solution preparation: used medicine is an analytical reagent, adopts the deionized water preparation.Take by weighing a certain amount of CuSO
4And ammoniacal liquor, mix the beaker that the solution that is mixed with 100ml places 200ml, wherein CuSO
4Be respectively 0.02M/L and 1.0M/L with the volumetric molar concentration of ammoniacal liquor;
2, the preparation of negatively charged ion precursor solution: take by weighing a certain amount of Na
2The solution that S is mixed with 100ml places beaker, Na
2The volumetric molar concentration of S is 0.06M/L;
3, priority process dilute sulphuric acid, the slide glass that ammoniacal liquor and dehydrated alcohol cleaned immerses in the mixed-cation solution and carries out surface adsorption, and the time is 20 seconds, immerses in the mobile deionized water container to clean 20 seconds again, then immerses negatively charged ion presoma Na
2Reaction is 20 seconds in the S solution, at last slide glass is used mobile washed with de-ionized water 20 seconds, finishes a continuous ionic layer absorption reaction circulation;
4, repeat on slide glass, to obtain the Cu that thickness is about 500nm with cocycle 100 times
2The S film.
Step 2, at Cu
2Deposit ZnSnS on the S film
xMembrane structure:
1, positively charged ion precursor solution preparation: used medicine is an analytical reagent, adopts the deionized water preparation.Take by weighing a certain amount of ZnSO
4And SnSO
4The solution that is mixed with 100ml places the beaker of 200ml, wherein ZnSO
4And SnSO
4Volumetric molar concentration is respectively 0.1M/L and 0.2M/L.The ammonium fluoride that adds 2M/L then;
2, the preparation of negatively charged ion precursor solution: take by weighing a certain amount of Na
2The solution that S is mixed with 100ml places beaker, Na
2The volumetric molar concentration of S is 0.05M/L;
3, depositing Cu
2The slide glass of S film immerses in the cationic solution and carries out surface adsorption, and the time is 20 seconds, immerses in the mobile deionized water container again and cleans 20 seconds, then immerses negatively charged ion presoma Na
2Reaction is 20 seconds in the S solution, uses the mobile washed with de-ionized water at last 20 seconds, finishes a continuous ionic layer absorption reaction circulation;
4, repeat with cocycle 100 times, at Cu
2Deposit thickness on the S film and be about the ZnSnS of 500nm
xFilm.
Step 3, thermal treatment:
Depositing Cu
2S film and ZnSnS
xThe slide glass of pellicular cascade preformed layer structure places argon gas and hydrogen sulfide (95%Ar+5%H
2S) the following 550 ℃ of heating of mixed atmosphere are 20 minutes, obtain copper-zinc-tin-sulfur film (Cu on slide glass
2ZnSnS
4).After testing, each composition of gained copper-zinc-tin-sulfur film meets stoichiometric ratio, film energy gap E
g=1.5eV, uptake factor are 10
5, resistivity is 4.5 Ω cm, carrier concentration is 3.1 * 10
18Cm
-3, the XRD of film, scanning electron microscope and Raman spectrum shown in accompanying drawing 4～6, are learnt by XRD and Raman analysis that respectively prepared sample is a copper tin tin sulphur, does not have other dephasign, equate as sulphur copper.
Claims (9)
1. the preparation method of a copper-zinc-tin-sulfur film, be adopt continuous ionic layer absorption reaction method with on the same substrate successively or alternately be immersed in positively charged ion precursor solution and the negatively charged ion precursor solution and prepare Cu
2SnS
xFilm and ZnS pellicular cascade preformed layer structure or Cu
2S film and ZnSnS
xPellicular cascade preformed layer structure is heat-treated then and is obtained copper-zinc-tin-sulfur film; Described alternately immersion, each soak time is 10～30 seconds, each back of soaking is with cleaning in the mobile deionized water 10～50 seconds; Contain at least a in copper, tin, the zine ion in the described positively charged ion precursor solution, described negatively charged ion precursor solution is selected from least a in sodium sulfide solution, potassium sulfide solution, the sulfuration ammonia solution; Described substrate is selected from a kind of in glass, PI, stainless steel substrates, molybdenum sheet, the titanium sheet.
2. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 1, it is characterized in that: the copper in the described positively charged ion precursor solution, tin, zine ion are obtained in deionized water by the compound dissolution of cupric tin, zinc, sulphur; The described Cu of containing compound is selected from least a in the halogenide that contains Cu, nitrate, vitriol, the acetate; Described stanniferous compound is selected from least a in the halogenide that contains Sn, nitrate, the vitriol; Described zinciferous compound is selected from least a in the halogenide that contains Zn, nitrate, vitriol, the acetate; Vitriol, nitrate, the halogenide of preferred Cu; Preferred Zn halogenide, vitriol, acetate; The halogenide, the vitriol that preferably contain Sn.
3. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 2 is characterized in that: adopt continuous ionic layer absorption reaction method to prepare Cu
2SnS
xFilm and ZnSnS
xDuring film, contain complexing agent in the described positively charged ion precursor solution, described complexing agent is selected from least a in tartrate, sodium tartrate, citric acid, trolamine, ammonium fluoride, the quadrol, and the total mol concentration of described complexing agent is 0.1～1M/L.
4. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 3 is characterized in that: adopt continuous ionic layer absorption reaction legal system to be equipped with Cu
2SnS
xDuring film, cupric ion and tin ion volumetric molar concentration are respectively 0.001～0.2M/L and 0.001～0.2M/L in the described positively charged ion precursor solution; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
5. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 2 is characterized in that: be equipped with Cu with continuous ionic layer absorption reaction legal system
2During the S film, described positively charged ion precursor solution cupric ion volumetric molar concentration is 0.001～0.2M/L, and adds ammoniacal liquor, and described ammoniacal liquor volumetric molar concentration is 0.1～5M/L; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
6. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 2, it is characterized in that: when being equipped with the ZnS film with continuous ionic layer absorption reaction legal system, described positively charged ion precursor solution zine ion volumetric molar concentration is 0.001～0.2M/L; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
7. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 3 is characterized in that: be equipped with ZnSnS with continuous ionic layer absorption reaction legal system
xDuring film, zine ion and tin ion volumetric molar concentration are respectively 0.001～0.2M/L and 0.001～0.2M/L in the described positively charged ion precursor solution; Described substrate cycle index 30～600 times in the positively charged ion precursor solution, making film thickness is 100～2400nm.
8. according to the preparation method of any described a kind of copper-zinc-tin-sulfur film of claim 1-7, it is characterized in that: the volumetric molar concentration of described negatively charged ion precursor solution is 0.05～0.2M/L.
9. the preparation method of a kind of copper-zinc-tin-sulfur film according to claim 8 is characterized in that: with the Cu of preparation
2SnS
xFilm and ZnS pellicular cascade or ZnSnS
xFilm and Cu
2The S pellicular cascade places under 200 ℃～600 ℃ sulfur-bearing atmosphere and annealed 5～60 minutes, obtains copper-zinc-tin-sulfur film; Described sulfur-bearing atmosphere is mixed evaporation selenium atmosphere, Ar+H for evaporation sulphur atmosphere, evaporation sulphur
2S atmosphere, N
2+ H
2At least a in the S atmosphere.
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