CN104120467A - Copper-zinc-tin film material with controllable components, copper-zinc-tin sulfenyl solar battery and preparation method of the two - Google Patents
Copper-zinc-tin film material with controllable components, copper-zinc-tin sulfenyl solar battery and preparation method of the two Download PDFInfo
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Abstract
The invention discloses a preparation method of a copper-zinc-tin film material. The preparation method comprises the following steps: (1) the copper-zinc-tin film material comprises at least three main metal elements of copper, zinc and tin; electroplate liquid contains any two main metal elements; and additive solution contains a third main metal element; (2) at least one conducting electrode serves as a first electrode in the electroplate liquid; and a film substrate to be plated serves as a second electrode; (3) when electricity is conducted between the first electrode and the second electrode, and the speed is controlled to add the additive solution, that is, films containing three metals of copper, zinc and tin are synchronously deposited to obtain a substrate deposited with the copper-zinc-tin metal film on the surface; and the copper-zinc-tin film material is obtained. In the preparation method of a copper-zinc-tin sulfenyl solar battery, a cadmium sulfide buffer layer, a ZnO film and an ITO film or an AZO film are deposited on the copper-zinc-tin film material in sequence to obtain the copper-zinc-tin sulfenyl solar battery after the step (4).
Description
Technical field
The present invention relates to the thin film solar cell in photoelectric material and technical field of new energies, be specially a kind of controlled copper zinc-tin thin-film material and copper-zinc-tin-sulfur based solar battery and both preparation methods thereof of forming.
Background technology
Along with the minimizing of the Nonrenewable energy resources reserves such as fossil oil, sustainable clean reproducible energy, as sun power, wind energy, bioenergy, tidal energies etc. have been subject to paying close attention to widely.Especially sun power, inexhaustible as one, the new forms of energy of environmentally safe, become with fastest developing speedly, and the field attracting most attention, is the effective means that solves world energy sources crisis now.Photovoltaic generation is the important means of utilizing sun power, therefore now more and more to the research of solar cell.
At present solar cell is mainly taking silicon single crystal and polysilicon as main, but production cost is too high, and light decay effect is obvious.Thin film solar cell is with the advantage of silicon solar cell efficiency of conversion height and cost cheapness, simultaneously high to photoabsorption coefficient, is a kind of more promising solar cell material.Copper indium gallium selenide film battery is that current technology is the most ripe, and most effective thin-film solar cells, but indium and gallium are rare and scatter elements is expensive and reserves are limited.At present most study, to be considered to most potential equivalent material be the copper-zinc-tin-sulfur film material that substitutes In and Ga with Zn and Sn, the high conversion efficiency of solar cell that at present prepared by its laboratory has reached 12.6%.
The preparation of copper-zinc-tin-sulfur film mainly contains two kinds of vacuum method and antivacuum methods.Vacuum method has magnetron sputtering method, thermal evaporation, and pulsed laser deposition etc., antivacuum method has electrochemical deposition, sol-gel, spray pyrolysis etc.The sample quality that comparatively speaking prepared by vacuum method is high, but the high condition harshness of process costs, but not vacuum method cost is low, less demanding to processing condition, thereby obtained larger attention.Wherein electrochemical deposition method has lot of advantages: as controlled in electrochemical process parameter, repeatability is high; Less demanding to experimental installation, cost is low, and room temperature can be carried out; Simple and fast, and thin film deposition is more even.
Electrochemically depositing copper-zinc-tin sulphur mainly contains two kinds of methods, the i.e. method of fractional steps and co-electrodeposition method at present.The method of fractional steps is that copper, zinc, three metals of tin are deposited in substrate successively, then vulcanizes.The advantage of this method is that three metallic solutions are stable, can repeatedly recycle, simple to operate.But the quality that the strict control of needs is every layer and thickness regulate the stoichiometric ratio of rete, and need to control the pattern of every layer, because coarse substrate meeting makes lower one deck metallic surface more coarse, also will consider the fringing effect of electrochemical deposition, working electrode substrate upper limb and center deposition variable thickness cause.Second method is co-electrodeposition method, is deposited in substrate simultaneously, and then vulcanizes synthetic copper-zinc-tin-sulfur film by three metals of copper zinc-tin.This method needs the strict relative concentration of controlling three metallic solutions of copper zinc-tin, the pH of solution, temperature and deposition voltage.Because the reduction potential gap of three metals of copper zinc-tin is larger, be therefore difficult to obtain the copper-zinc-tin-sulfur film of proper ratio, and three kinds of metal-salts mix, stability of solution is not high.Two kinds of methods comparatively speaking, film prepared by the method for fractional steps, Composition Control is good but crystallinity is bad, and the bad control of codeposition composition but good crystallinity; Therefore all cannot meet preparation and the service requirements of copper-zinc-tin-sulfur film.
Summary of the invention
For the problem proposing in prior art, the invention provides one and not only can accurately control deposition ratio, and excellent in crystallinity, form controlled copper zinc-tin thin-film material and copper-zinc-tin-sulfur based solar battery and both preparation methods thereof.
The present invention is achieved through the following technical solutions:
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, comprises the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin; In electroplate liquid, contain any two kinds in three kinds of base metal elements; Annex solution contains the third base metal element lacking in described electroplate liquid;
2) in electroplate liquid, have at least one conductive electrode as the first electrode, film-substrate to be plated is as the second electrode; Described film-substrate to be plated is the substrate that conductive substrates or surface coverage have conductive film;
3) while energising between the first electrode and the second electrode, speed control adds annex solution, starts to deposit the film of cupric, zinc and three kinds of metals of tin simultaneously, obtains the substrate of copper-depositing on surface zinc-tin metallic film, is copper zinc-tin thin-film material; In electroplating process, relative the first electrode of the second electropotential is for negative.
Preferably, in step 3) afterwards, the substrate of copper-depositing on surface zinc-tin metallic film is heated at 200～400 DEG C of temperature and processes and within 20～60 minutes, obtain potin thin-film material.
Preferably, in step 3) afterwards, copper zinc-tin thin-film material or potin thin-film material are exposed to sulfur-bearing atmosphere, be heated at 400～700 DEG C of temperature and process 1～40 minute, prepare copper-zinc-tin-sulfur film material.
Preferably, in step 3) afterwards, copper zinc-tin thin-film material or potin thin-film material are exposed to sulfur-bearing and selenium atmosphere, be heated at 400～700 DEG C of temperature and process 1～40 minute, prepare copper zinc tin sulfur selenium thin-film material; The ratio of sulphur and selenium in thin-film material, regulates by the ratio of sulphur in controlled atmosphere and selenium.
Preferably, step 1) in electroplate liquid be dissolved in water by the metal-salt of zinc-tin or copper tin or zinc-tin and complex compound and make, salt concn scope is separately 0.01～1M, complex compound is one or more in oxyhydroxide, thiosulphate, sulphite, Citrate trianion, pyrophosphate salt, tartrate, tartrate and prussiate, and complex concentration scope is 0.01～0.5M.
Further, step 1) in annex solution be dissolved in water by the third plating metal salt and complex compound and make, salt concn scope is 0.01～1M, complex compound is one or more in oxyhydroxide, thiosulphate, sulphite, Citrate trianion, pyrophosphate salt, tartrate, tartrate and prussiate, and complex concentration scope is 0.1～0.5M.
Preferably, step 2) in, the plated film part that adds total amount submergence film-substrate to be plated of electroplate liquid and annex solution; Film-substrate to be plated is connected with negative electrode, and the first electrode is connected with anode, is independently provided with reference electrode in electroplate liquid; Before electroplating, regulate electroplate liquid pH value to 2～6; When plating, between the first electrode and the second electrode, apply voltage-10～0V, distance is 0.2～20cm, and when plating, electroplate liquid keeps the constant temperature of 20-80 DEG C.
Preferably, the surface coverage of employing has the substrate of conductive film, and conductive film is that thickness is metal or the metal oxide film of 0.1～10 micron.
Further, film-substrate to be plated is rigid substrate, and rigid substrate comprises metal substrate, silicon chip and is coated with glass substrate or the ceramic substrate of conductive film.
Further again, metal substrate comprises copper sheet, aluminium flake and stainless steel substrates; Described glass substrate comprises the glass that is coated with FTO and the glass that is coated with ITO.
Further, film-substrate to be plated is the flexible substrate that comprises tinsel and polymer membrane.
Further again, flexible substrate by electroplate liquid, is prepared copper zinc-tin metallic film in reel-to-reel mode in flexible substrate.
The present invention is a kind of forms controlled copper zinc-tin thin-film material, is made by the preparation method of above-described any one copper zinc-tin thin-film material.
Preferably, the thickness of copper zinc-tin thin-film material is 500～5000 nanometers.
Further, the thickness of copper zinc-tin thin-film material is 1000～3000 nanometers, and copper zinc-tin thickness of metal film is 700～1500 nanometers.
The preparation method of a kind of copper-zinc-tin-sulfur based solar battery of the present invention, in the preparation method's of above any one copper zinc-tin thin-film material step 3) afterwards, obtain copper-zinc-tin-sulfur based solar battery also comprise the steps: to deposit successively Cadmium Sulfide buffer layer and ZnO film and ito thin film or AZO film on copper zinc-tin thin-film material after.
A kind of copper-zinc-tin-sulfur based solar battery of the present invention, is made by the preparation method of copper-zinc-tin-sulfur based solar battery of the present invention.
Compared with prior art, the present invention has following useful technique effect:
The preparation method of copper zinc-tin thin-film material of the present invention, contains binary metal ion-conductance plating solution by configuration, then controls drop rate and add the annex solution containing the third metallic element in the process of deposition, deposition when having ensured three kinds of metallic elements.The nonuniform deposition bringing by the potential difference control that adds speed having been reduced between three kinds of metallic elements, changes ternary codeposition into the third metallic solution add-on controlled binary codeposition, makes the control of galvanic deposit increase a dimension.Simple and convenient, stable performance, has prepared the controlled copper zinc-tin thin-film material of metal ratio, is applicable to preparation and the industrial applications of follow-up solar cell device.Because by three kinds of metallic elements, mixed deposits are on substrate simultaneously, compared with the technique of electroplating three kinds of metallic elements with lamination, the present invention, without the long range diffusion of element, has reduced the needed time of subsequent disposal.
Further, by the alloying activation treatment to film-substrate to be plated, make its condition of surface can be good at realizing the initial stage nucleation of film and strengthening bonding force, better improved the quality of thin-film material.
Further, by carry out heat treated in the atmosphere of sulfur-bearing or sulfur-bearing and selenium, can obtain corresponding copper zinc-tin thin-film material, adapt to different user demands, on the basis of alloying heat treated, in the at high temperature short period of time, complete processing, better improve the photoelectric properties of thin-film material, product stability and high efficiency, and can be by the ratio of sulphur in controlled atmosphere or selenium, the object that reaches adjusting, realizes controllable operating.
Further, the present invention is dissolved jointly by metal-salt and complex compound, and use vitriol or other salts that easily decomposition is volatilized, thereby avoid the impact of other foreign ions on film morphology and battery efficiency in the final quaternary sulfide producing, ensure the quality of the film of preparation, be easy to large-area industry preparation, with low cost.
Further, the present invention limits each influence factor in electrodeposition process, has finally obtained the experiment condition of optimal deposition metallic film by the restriction of temperature, pH, electrolyte concentration, complexing ion concentration and the deposition voltage of electrochemical deposition preferably.Bath temperature can affect the current efficiency of metal in the time of cathodic deposition; The quality of forming film of sedimentation potential alloy coating has remarkably influenced; Stirring, additive, concentration of metal ions and complexing agent concentration can directly have influence on the component of alloy layer.This programme adopts three-electrode system to carry out electrochemical deposition in addition, and system is more stable, and the result of acquisition is more credible.
Further, use the rigid substrate such as silicon chip or glass, pattern, nucleation, growth and preferred orientation to metal back electrode and copper-zinc-tin-sulfur film produce Beneficial Effect, and ensure that in reprocessing, especially the soda-lime glass substrate of subsequent product, sodium element is conducive to grow high-quality copper zinc-tin-sulfur film to upper strata diffusion.
Further, prepare copper-zinc-tin-sulfur film by flexible substrate, can make the solar cell obtaining reach high mass-power ratio, and manufacture cost is low, is suitable for architecture-integral, the solar cell being particularly suitable on uneven roof uses.The flexible battery of making can cut into any shape and size, also can make photovoltaic tiles simultaneously; Be applicable to large-scale volume to volume explained hereafter, and have foldability and non-friable characteristic, practical application is strong.
Further, volume to volume mode deposits prepares copper zinc selenium metallic film, contribute to the industrialization of copper zinc-tin based thin film solar cell, by the preferably control of the rate of addition of pH, deposition voltage, stir speed (S.S.), the third solution, ensure the preparation condition of optimal deposition copper zinc selenium metallic film, be convenient to suitability for industrialized production.
The present invention forms controlled copper zinc-tin thin-film material, by the restriction of copper zinc selenium thickness of metal film, for follow-up battery device preparation provides good basis, is conducive to improve battery efficiency.
Copper-zinc-tin-sulfur film solar cell of the present invention and preparation method thereof, on the basis of the thin-film material of preparing, by deposition and control to buffer layer and conductive window layer, the preparation of solar cell and the lifting of performance thereof are completed, the method processing is simple, and membrane quality is good.
Brief description of the drawings
Fig. 1 is preparation technology's schema of the copper-zinc-tin-sulfur film material described in example of the present invention.
Fig. 2 is the SEM figure that makes copper-zinc-tin-sulfur film material in example of the present invention.
Fig. 3 is the XRD figure that makes copper-zinc-tin-sulfur film material in example of the present invention.
Fig. 4 is the Raman figure that makes copper-zinc-tin-sulfur film material in example of the present invention.
Fig. 5 is the copper-zinc-tin-sulfur film battery section S EM figure doing in molybdenum glass substrate in example of the present invention.
Fig. 6 is the I-V figure that makes copper-zinc-tin-sulfur film solar cell in example of the present invention.
Fig. 7 be in example of the present invention copper zinc-tin thin-film material with the preparation facilities schematic diagram of reel-to-reel mode.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and the explanation of the invention is not limited.
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, it comprises the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin; In electroplate liquid, contain any two kinds in three kinds of base metal elements; Annex solution contains the third base metal element lacking in described electroplate liquid;
2) in electroplate liquid, have at least one conductive electrode as the first electrode, film-substrate to be plated is as the second electrode; Described film-substrate to be plated is the substrate that conductive substrates or surface coverage have conductive film;
3) while energising between the first electrode and the second electrode, speed control adds annex solution, starts to deposit the film of cupric, zinc and three kinds of metals of tin simultaneously, obtains the substrate of copper-depositing on surface zinc-tin metallic film, is copper zinc-tin thin-film material; In electroplating process, relative the first electrode of the second electropotential is for negative.
In step 3) after, the substrate of copper-depositing on surface zinc-tin metallic film can be heated at 200～400 DEG C of temperature and process and within 20～60 minutes, obtain potin thin-film material; Copper zinc-tin thin-film material or potin thin-film material can also be exposed to sulfur-bearing atmosphere, be heated at 400～700 DEG C of temperature 1～40 minute, prepare copper-zinc-tin-sulfur film material.Also copper zinc-tin thin-film material maybe can be exposed to potin thin-film material sulfur-bearing and selenium atmosphere, is heated at 400～700 DEG C of temperature 1～40 minute, prepares copper zinc tin sulfur selenium thin-film material; The ratio of sulphur and selenium in thin-film material, is regulated by the ratio of controlling in sulphur and selenium atmosphere.Preparation technology's schema as shown in Figure 1, by the properties of the copper-zinc-tin-sulfur film material that as above method obtains as shown in Fig. 2-Fig. 6.
Fig. 2 is SEM figure, the as can be seen from the figure copper-zinc-tin-sulfur film surfacing densification after annealing, uniform particles distributes, and between particle almost without cavity, be applicable to follow-up battery and prepare.
Fig. 3 is XRD figure: for adopting the CZTS film of electrochemical deposition, sulfuration annealing plays vital effect.Can find out from XRD diffraction peak, all films all present (112) that CZTS is stronger, (211), (200), and (312) characteristic peak (220), in addition, also found (110) and (211) diffraction peak of Mo substrate, without the diffraction peak of other Binary-phase impurity.Due to Cu
2znSnS
4, ZnS and Cu
2snS
3diffraction peak very nearly the same, therefore further adopt Raman to test.
Fig. 4 is Raman figure: at 251cm
-1, 287cm
-1, 338cm
-1and 368cm
-1the vibration peak at place is all corresponding is the thing phase of CZTS, and this is identical with the analytical results of XRD.ZnS and Cu do not detected
2snS
3thing phase, illustrate that CZTS thing prepared by this method compares pure.
Fig. 5 is the SEM sectional view of copper-zinc-tin-sulfur film battery: the cross section of the copper-zinc-tin-sulfur film solar cell being obtained by preparation method of the present invention as shown in the figure, back electrode molybdenum layer thickness is about 1 μ m as seen from the figure, between Mo and CZTS, there is the moly-sulfide of 100nm left and right to generate, the CZTS absorber thickness of uniform particles densification is about 800nm, is followed successively by buffer layer CdS and i-ZnO and AZO above.
Fig. 6 is device efficiency analysis chart, and the structure of the CZTS thin-film solar cells being obtained by preparation method of the present invention is Mo/CZTS/CdS/i-ZnO/AZO, at room temperature AM1.5 and 1000W/m
2the I-V rational curve recording under condition as shown in the figure.Reported first the CZTS hull cell prepared of the method, battery efficiency is 1.60%.
Concrete preparation process is as following instance 1-35.
Example 1
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration zinc-tin binary metal mixing solutions does electrolytic solution: 0.07M zinc sulfate, and the tin sulphate of 0.05M, Trisodium Citrate complexing agent, pH is 3.Configure the third metal salt solution and do annex solution: 0.4M copper sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 15ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-1.7V, depositing time 10min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 2
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper zinc binary metal mixing solutions: 0.08M zinc sulfate, the copper sulfate of 0.01M, Trisodium Citrate complexing agent, pH is 6.Configure the third metal salt solution and do annex solution: 0.3M tin sulphate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 10ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-1.7V, depositing time 7min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 3
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper tin binary metal mixing solutions: 0.02M copper sulfate, the tin sulphate of 0.01M, Trisodium Citrate complexing agent, pH is 5.Configure the third metal salt solution and do annex solution: 0.3M zinc sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 15ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-1.75V, depositing time 15min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 4
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration zinc-tin binary metal mixing solutions does electrolytic solution: 0.08M zinc sulfate, and the tin sulphate of 0.01M, Trisodium Citrate complexing agent, pH is 4.Configure the third metal salt solution and do annex solution: 0.3M copper sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 8ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-1.75V, depositing time 8min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 5
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper zinc binary metal mixing solutions: 0.01M zinc sulfate, the copper sulfate of 0.05M, Trisodium Citrate complexing agent, pH is 3.Configure the third metal salt solution and do annex solution: 0.5M tin sulphate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, and add-on is 3ml/min, adopts the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is 0V, depositing time 14min, complete the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 6
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration zinc-tin binary metal mixing solutions does electrolytic solution: 0.8M zinc sulfate, and the tin sulphate of 0.6M, Trisodium Citrate complexing agent, pH is 5.Configure the third metal salt solution and do annex solution: 1M copper sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 0.26ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-2V, depositing time 12min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 7
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper tin binary metal mixing solutions: 0.4M copper sulfate, the tin sulphate of 0.7M, Trisodium Citrate complexing agent, pH is 2.Configure the third metal salt solution and do annex solution: 1M zinc sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 0.14ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-4V, depositing time 9min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 8
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper zinc binary metal mixing solutions: 0.06M zinc sulfate, the copper sulfate of 0.13M, Trisodium Citrate complexing agent, pH is 4.Configure the third metal salt solution and do annex solution: 1M tin sulphate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 0.10ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-3V, depositing time 11min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 9
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper zinc binary metal mixing solutions: 0.41M zinc sulfate, the copper sulfate of 0.75M, Trisodium Citrate complexing agent, pH is 4.Configure the third metal salt solution and do annex solution: 0.01M tin sulphate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 13ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-10V, depositing time 6min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 10
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration zinc-tin binary metal mixing solutions does electrolytic solution: 0.37M zinc sulfate, and the tin sulphate of 0.26M, Trisodium Citrate complexing agent, pH is 6.Configure the third metal salt solution and do annex solution: 0.01M copper sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 14ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-7V, depositing time 13min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 11
The preparation method of a kind of copper zinc-tin of the present invention thin-film material, step is as follows:
Configuration copper tin binary metal mixing solutions: 0.50M copper sulfate, the tin sulphate of 0.65M, Trisodium Citrate complexing agent, pH is 3.Configure the third metal salt solution and do annex solution: 0.01M zinc sulfate, Trisodium Citrate is complexing agent.Be connected and be placed in electrolytic solution using substrate as the second electrode with as the conductive electrode of the first electrode, relative first electrode of current potential of the second electrode is for negative.Speed control adds annex solution, add-on is 1.2ml/min, adopt the same time of set potential to start deposited copper, zinc, three kinds of metals of tin, form metallic film, current potential is-9V, depositing time 5min, completes the substrate that obtains copper-depositing on surface zinc-tin metallic film after plating, i.e. copper zinc-tin thin-film material.
Example 12
In example 1-11, any one sulfate ion in zinc sulfate, tin sulphate and copper sulfate can both be replaced and form corresponding metal-salt by other acid ions, carry out remaining operation, wherein preferred acid ion is nitrate ion and chlorion, and in the time once electroplating together, zinc, tin and copper can carry out in conjunction with different acid ions.
Embodiment 13
In example 1-12, complex compound in electroplate liquid and annex solution all can adopt one or more in oxyhydroxide, thiosulphate, sulphite, Citrate trianion, pyrophosphate salt, tartrate, tartrate and prussiate including Trisodium Citrate, preferably 0.01～5M of the concentration of complex compound in electroplate liquid, preferably 0.1～5M of the concentration of complex compound in annex solution, concrete complex compound type and concentration all can be selected according to the solvability of corresponding metal-salt.
Example 14
In example 1-13, when speed control adds annex solution, annex solution adds fashionable peristaltic pump, liquid-transfering gun, drop-burette or the graduated cylinder of can adopting and carries out interval or that continue or adding dropwise, ensure that wherein adding rate and the sedimentation rate of the third base metal element reach running balance, the speed of adding reaches and equates with the speed of deposition, the demand when amount adding can meet its deposition, makes to add speed to destroy the crystallinity of stability of solution or three kinds of base metal elements but can not exceed its demand.Wherein, by controlling drop rate, make the sedimentation rate that adds the ion that speed and galvanic deposit get on of annex solution reach running balance, deposition is controlled accurate, deposit film is evenly level and smooth.
Example 15
In example 1-11,, and be connected with anode as long as to finally obtaining to such an extent that the copper zinc-tin thin-film material electrode that can not exert an influence all can adopt as the conductive electrode of the first electrode, wherein preferably adopt platinum electrode or Graphite Electrodes in noble electrode; The second electrode is connected with negative electrode, and the first electrode and the second interelectrode distance are set up an office according to practical situation and select, preferably at 0.2～20cm.
Example 16
At example 1-11, and on example 15 bases, in the time electroplating, can also preferably add reference electrode that reference potential is provided, reference electrode preferably adopts mercurous chloride electrode or silver-silver chloride electrode, in the time of electroplate liquid, keep the temperature of electroplate liquid at 20～80 DEG C, this preferred embodiment is realized the temperature of maintenance with water bath with thermostatic control.
Example 17
As shown in Figure 1, in example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate ultrapure water that takes out depositing copper-zinc-tin metallic film washes away the foreign ion adhering on surface, and dry, preferably adopts nitrogen to dry up; Copper zinc-tin metallic film is thoroughly cleaned, reduce the impact of foreign ion on film quality and follow-up battery efficiency in plating solution, improved the quality of thin-film material.Can in tube furnace or other equipment, carry out anneal, metallic film annealing temperature is 250 DEG C, and heat-up rate is 10 DEG C/s, and soaking time is 30min, and annealing furnace internal gas pressure is 0.01atm, and gas flow is 40sccm, naturally cooling.
Example 18
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate ultrapure water that takes out depositing copper-zinc-tin metallic film washes away the foreign ion adhering on surface, and dry, preferably adopt nitrogen to dry up; Can in tube furnace or other equipment, carry out anneal, metallic film annealing temperature is 330 DEG C, and heat-up rate is 10 DEG C/s, and soaking time is 20min, and annealing furnace internal gas pressure is 0.01atm, and gas flow is 50sccm, naturally cooling.
Example 19
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate that takes out depositing copper-zinc-tin metallic film carries out anneal in tube furnace or other equipment, metallic film annealing temperature is 380 DEG C, heat-up rate is 10 DEG C/s, and soaking time is 40min, and annealing furnace internal gas pressure is 0.03atm, gas flow is 60sccm, naturally cooling.
Example 20
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate ultrapure water that takes out depositing copper-zinc-tin metallic film washes away the foreign ion adhering on surface, and dry, preferably adopt nitrogen to dry up; Can in tube furnace or other equipment, carry out anneal, metallic film annealing temperature is 300 DEG C, and heat-up rate is 10 DEG C/s, and soaking time is 20min, and annealing furnace internal gas pressure is 0.03atm, and gas flow is 50sccm, naturally cooling.
Example 21
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate ultrapure water that takes out depositing copper-zinc-tin metallic film washes away the foreign ion adhering on surface, and dry, preferably adopt nitrogen to dry up; Can in tube furnace or other equipment, carry out anneal, metallic film annealing temperature is 400 DEG C, and heat-up rate is 10 DEG C/s, and soaking time is 50min, and annealing furnace internal gas pressure is 0.02atm, and gas flow is 40sccm, naturally cooling.
Example 22
In example 1-11, the substrate of copper-depositing on surface zinc-tin metallic film is first carried out to heat treated and obtain potin thin-film material, namely carry out alloying annealing, specific as follows, the substrate ultrapure water that takes out depositing copper-zinc-tin metallic film washes away the foreign ion adhering on surface, and dry, preferably adopt nitrogen to dry up; Can in tube furnace or other equipment, carry out anneal, metallic film annealing temperature is 200 DEG C, and heat-up rate is 10 DEG C/s, and soaking time is 60min, and annealing furnace internal gas pressure is 0.02atm, and gas flow is 50sccm, naturally cooling.
Example 23
In example 1-22, copper zinc-tin thin-film material or potin thin-film material are exposed to sulfur-bearing atmosphere, when pyroprocessing, heat treated in the tube furnace of argon gas atmosphere; When processing, temperature is 585 DEG C, heat-up rate is 5 DEG C/min, soaking time is 30 minutes, and annealing furnace internal gas pressure is 0.1atm, and gas flow is 50sccm, the sulfiding gas adopting is sulfur vapor, sulphur powder is put in graphite, more together put into and in tube furnace, participate in heat treated, form sulfur vapor.
Example 24
In example 1-22, when copper zinc-tin thin-film material or potin thin-film material are exposed in sulfur-bearing atmosphere to pyroprocessing, heat treated in the tube furnace of nitrogen atmosphere; When processing, sulfuration annealing temperature is 600 DEG C, and heat-up rate is 10 DEG C/min, and soaking time is 10 minutes, and annealing furnace internal gas pressure is 0.1atm, and gas flow is 100sccm, and the sulfiding gas of employing is hydrogen sulfide.
Example 25
In example 1-22, when copper zinc-tin thin-film material or potin thin-film material are exposed in sulfur-bearing atmosphere to pyroprocessing, heat treated in tube furnace; When processing, sulfuration annealing temperature is 620 DEG C, and heat-up rate is 10 DEG C/min, and soaking time is 20 minutes, and annealing furnace internal gas pressure is 0.2atm, and gas flow is 80sccm, and the sulfiding gas of employing is tin sulfide.
Example 26
In example 1-22, when copper zinc-tin thin-film material or potin thin-film material are exposed in sulfur-bearing atmosphere to pyroprocessing, heat treated in the tube furnace of argon gas atmosphere; When processing, sulfuration annealing temperature is 620 DEG C, and heat-up rate is 10 DEG C/min, and soaking time is 25 minutes, and annealing furnace internal gas pressure is 0.2atm, and gas flow is 90sccm, and the sulfiding gas of employing is hydrogen sulfide.
Example 27
In example 1-22, when copper zinc-tin thin-film material or potin thin-film material are exposed in sulfur-bearing atmosphere to pyroprocessing, put it in the graphite that is added with sulphur powder heat treated in tube furnace; When processing, temperature is 700 DEG C, and heat-up rate is 5 DEG C/min, and soaking time is 1 minute, and annealing furnace internal gas pressure is 0.15atm, and gas flow is 60sccm.
Example 28
In example 1-22, when copper zinc-tin thin-film material or potin thin-film material are exposed in sulfur-bearing atmosphere to pyroprocessing, heat treated in the tube furnace of nitrogen atmosphere; When processing, sulfuration annealing temperature is 400 DEG C, and heat-up rate is 15 DEG C/min, and soaking time is 40 minutes, and annealing furnace internal gas pressure is 0.15atm, and gas flow is 70sccm, and the sulfiding gas of employing is tin sulfide.
Example 29
In example 1-11, and in example 17-22, by copper zinc-tin thin-film material or or potin thin-film material be placed in sulfur-bearing and selenium atmosphere and be heated to high temperature and process, thereby can prepare the copper zinc tin sulfur selenium thin-film material that performance is more superior, condition when processing is as shown in embodiment 23-28; Wherein, sulphur powder can be replaced by the sulphur powder and the selenium powder that mix, jointly puts into graphite, then puts into tube furnace and heat; Form the mixed vapour of sulphur and selenium; When sulphur adds fashionablely by hydrogen sulfide and tin sulfide, selenium also can add by the form of selenium steam; Wherein pass through the control to sulphur and selenium different content, thereby can regulate the content of sulphur and selenium in copper zinc tin sulfur selenium thin-film material, thereby meet different user demands.
Example 30
In example 1-29, film-substrate to be plated adopts conductive substrates, this example taking substrate as tinsel and the flexible substrate of polymer membrane be example, preferably adopt flexible stainless steel, by substrate, through acetone, ethanol, deionized water, ultrasonic 30 minutes post-dryings are for subsequent use respectively; Can also electrochemical deposition one deck molybdenum on substrate, thickness is about 1 micron.
Example 31
In example 30, film-substrate to be plated adopts conductive substrates, this example taking substrate as tinsel and the flexible substrate of polymer membrane be example, preferably adopt flexible stainless steel, can, by the preparation facilities of reel-to-reel mode as shown in Figure 7, prepare copper zinc-tin thin-film material of the present invention.
Example 32
In example 1-29, film-substrate to be plated adopts conductive substrates, this example taking substrate as metal substrate, silicon chip and be coated with the glass substrate of conductive film or the rigid substrate of ceramic substrate is example, preferred simple glass, by glass substrate, through acetone, ethanol, deionized water, ultrasonic 30 minutes post-dryings are for subsequent use respectively, in glass substrate, need electron beam evaporation plating one deck molybdenum, thickness is about 1 micron; Molybdenum can also be replaced with to the metal that comprises gold, copper and aluminium, the thickness of metal is 0.1～10 micron.By the back contact that utilizes molybdenum, gold, copper and aluminium film to form, making has good ohmic contact between itself and absorption layer, has reduced interfacial state between the two; Utilize its good conductivity to ensure the characteristics of output power that it is good; Simultaneously with its on copper zinc-tin absorption layer material there is not chemical reaction, guaranteed the stability of thin-film material, can also be good be attached on film-substrate to be plated.
Example 33
In example 1-29, film-substrate to be plated adopts conductive substrates, this example taking substrate as metal substrate, silicon chip and be coated with the glass substrate of conductive film or the rigid substrate of ceramic substrate is example, preferred soda-lime glass, by substrate, through acetone, ethanol, deionized water, ultrasonic 30 minutes post-dryings are for subsequent use respectively, on substrate, by magnetron sputtering method sputter layer of copper, thickness is about 1 micron; Copper can also be replaced with to the metal oxide that comprises ITO, FTO and AZO, the thickness of metal oxide is 0.1～10 micron.
Example 34
In example 1-29, film-substrate to be plated adopts conductive substrates, this example taking substrate as metal substrate, silicon chip and be coated with the glass substrate of conductive film or the rigid substrate of ceramic substrate is example, preferably molybdenum plate, by substrate, through acetone, ethanol, deionized water, ultrasonic 30 minutes post-dryings are for subsequent use respectively.SEM as shown in Figure 2 figure, the as can be seen from the figure smooth densification of film surface after sulfuration annealing, uniform particles distributes, and between particle almost without cavity, be applicable to follow-up battery and prepare.XRD figure as shown in Figure 3, for adopting CZTS (copper-zinc-tin-sulfur) film of electrochemical deposition, the effect that is heated to pyroprocessing in sulfur-bearing atmosphere is very important, namely the sulfuration anneal to CZTS film.Can find out from XRD diffraction peak, all films all present (112) that CZTS is stronger, (211), (200), and (312) characteristic peak (220), in addition, also found (110) and (211) diffraction peak of Mo substrate.Due to Cu
2znSnS
4, ZnS and Cu
2snS
3diffraction peak very nearly the same, therefore further adopt Raman to test.As shown in Figure 4, in Raman figure at 251cm
-1, 287cm
-1, 338cm
-1and 368cm
-1the vibration peak at place is all corresponding is the thing phase of CZTS, and this is identical with the analytical results of XRD.ZnS and Cu do not detected
2snS
3thing phase, illustrate that CZTS thing phase purity prepared by the inventive method is high.The analytical results of other examples is identical, or else repeats.
Example 35
On the basis of example 1-34, prepare the controlled copper zinc-tin thin-film material of composition, wherein the thickness of copper zinc-tin thin-film material is 500～5000 nanometers; In this preferred embodiment, taking the thickness of copper zinc-tin thin-film material as 1000～3000 nanometers, copper zinc-tin thickness of metal film is 700～1500 nanometers.
Example 36
On the basis of example 1-34, then can obtain as follows copper zinc-tin thin-film solar cells, concrete steps are to deposit Cadmium Sulfide buffer layer on copper zinc-tin film; On Cadmium Sulfide buffer layer, after deposit transparent conductive oxide i-ZnO film and ito thin film or AZO film, obtain copper-zinc-tin-sulfur film solar cell respectively.
Example 37
In example 36, the thickness of Cadmium Sulfide buffer layer is 40～150 nanometers, adopts chemical bath method to deposit.
Example 38
In example 36, the deposit thickness of transparent conductive oxide i-ZnO film is 50～150 nanometers; On Cadmium Sulfide buffer layer, deposit thickness is the AZO film of 300～900 nanometers; I-ZnO film and AZO film adopt magnetron sputtering method to deposit.Wherein, taking the molybdenum glass described in example 34 as basis, then deposit i-ZnO film and AZO film and obtain obtaining the SEM figure of copper-zinc-tin-sulfur film solar cell, as shown in Figure 5; Its I-V schemes as shown in Figure 6, and the battery device of the Mo glass/CZTS/CdS/i-ZnO/AZO structure of preparing with the CZTS film absorption layer after the annealing of this experiment condition, at room temperature AM1.5 and 1000W/m
2the I-V rational curve of the device recording under condition, test result is as follows: open circuit voltage (Voc) is 466mV, short-circuit current density (J
sc) be 8.05mA/cm
2, packing factor (FF) is 42.04%.Battery efficiency is 1.60%, obtains first battery efficiency prepared by the method for the invention.
Example 39
In example 36, the deposit thickness of transparent conductive oxide i-ZnO film is 50～150 nanometers; On Cadmium Sulfide buffer layer, deposit thickness is the ito thin film of 50～250 nanometers; I-ZnO film and ito thin film adopt magnetron sputtering method to deposit.
The above, be only preferred embodiment of the present invention, not the present invention done to any pro forma restriction.Any those of ordinary skill in the art, are not departing from technical solution of the present invention scope situation, all can utilize technology contents described above to make many possible variations and modification to technical solution of the present invention, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content that does not depart from technical solution of the present invention, a technology of the present invention, to any change made for any of the above embodiments or modification, all belongs to the protection domain of the technical program.
Claims (17)
1. a preparation method for copper zinc-tin thin-film material, is characterized in that, comprises the steps:
1) copper zinc-tin thin-film material contains at least copper, zinc and three kinds of base metal elements of tin; In electroplate liquid, contain any two kinds in three kinds of base metal elements; Annex solution contains the third base metal element lacking in described electroplate liquid;
2) in electroplate liquid, have at least one conductive electrode as the first electrode, film-substrate to be plated is as the second electrode; Described film-substrate to be plated is the substrate that conductive substrates or surface coverage have conductive film;
3) while energising between the first electrode and the second electrode, speed control adds annex solution, starts to deposit the film of cupric, zinc and three kinds of metals of tin simultaneously, obtains the substrate of copper-depositing on surface zinc-tin metallic film, is copper zinc-tin thin-film material; In electroplating process, relative the first electrode of the second electropotential is for negative.
2. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1, it is characterized in that, in step 3) afterwards, the substrate of copper-depositing on surface zinc-tin metallic film is heated at 200～400 DEG C of temperature and processes and within 20～60 minutes, obtain potin thin-film material.
3. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1 or 2, it is characterized in that, in step 3) afterwards, copper zinc-tin thin-film material or potin thin-film material are exposed to sulfur-bearing atmosphere, be heated at 400～700 DEG C of temperature and process 1～40 minute, prepare copper-zinc-tin-sulfur film material.
4. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1 or 2, it is characterized in that, in step 3) afterwards, copper zinc-tin thin-film material or potin thin-film material are exposed to sulfur-bearing and selenium atmosphere, be heated at 400～700 DEG C of temperature and process 1～40 minute, prepare copper zinc tin sulfur selenium thin-film material; The ratio of sulphur and selenium in thin-film material, regulates by the ratio of sulphur in controlled atmosphere and selenium.
5. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1, it is characterized in that, step 1) in electroplate liquid be dissolved in water by the metal-salt of zinc-tin or copper tin or zinc-tin and complex compound and make, salt concn scope is separately 0.01～1M, complex compound is one or more in oxyhydroxide, thiosulphate, sulphite, Citrate trianion, pyrophosphate salt, tartrate, tartrate and prussiate, and complex concentration scope is 0.01～0.5M.
6. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1 or 5, it is characterized in that, step 1) in annex solution be dissolved in water by the third plating metal salt and complex compound and make, salt concn scope is 0.01～1M, complex compound is one or more in oxyhydroxide, thiosulphate, sulphite, Citrate trianion, pyrophosphate salt, tartrate, tartrate and prussiate, and complex concentration scope is 0.1～0.5M.
7. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1, it is characterized in that step 2) in, the plated film part that adds total amount submergence film-substrate to be plated of electroplate liquid and annex solution; Film-substrate to be plated is connected with negative electrode, and the first electrode is connected with anode, is independently provided with reference electrode in electroplate liquid; Before electroplating, regulate electroplate liquid pH value to 2～6; When plating, between the first electrode and the second electrode, apply voltage-10～0V, distance is 0.2～20cm, and when plating, electroplate liquid keeps the constant temperature of 20-80 DEG C.
8. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1, it is characterized in that, the surface coverage of employing has the substrate of conductive film, and conductive film is that thickness is metal or the metal oxide film of 0.1～10 micron.
9. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1 or 8, it is characterized in that, described film-substrate to be plated is rigid substrate, and rigid substrate comprises metal substrate, silicon chip and is coated with glass substrate or the ceramic substrate of conductive film.
10. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 9, it is characterized in that, described metal substrate comprises copper sheet, aluminium flake and stainless steel substrates; Described glass substrate comprises the glass that is coated with FTO and the glass that is coated with ITO.
11. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 1 or 8, it is characterized in that, described film-substrate to be plated is the flexible substrate that comprises tinsel and polymer membrane.
12. according to the preparation method of a kind of copper zinc-tin thin-film material described in claim 11, it is characterized in that, described flexible substrate by electroplate liquid, is prepared copper zinc-tin metallic film in reel-to-reel mode in flexible substrate.
13. 1 kinds of copper zinc-tin thin-film materials that composition is controlled, is characterized in that, are made by the preparation method of any one copper zinc-tin thin-film material in claim 1～12.
14. a kind of controlled copper zinc-tin thin-film materials that form according to claim 13, is characterized in that, the thickness of copper zinc-tin thin-film material is 500～5000 nanometers.
15. a kind of controlled copper zinc-tin thin-film materials that form according to claim 14, is characterized in that, the thickness of copper zinc-tin thin-film material is 1000～3000 nanometers, and copper zinc-tin thickness of metal film is 700～1500 nanometers.
The preparation method of 16. 1 kinds of copper-zinc-tin-sulfur based solar batteries, it is characterized in that, the preparation method's of a kind of copper zinc-tin thin-film material in claim 1～12 described in any one step 3) afterwards, obtain copper-zinc-tin-sulfur based solar battery also comprise the steps: to deposit successively Cadmium Sulfide buffer layer and ZnO film and ito thin film or AZO film on copper zinc-tin thin-film material after.
17. 1 kinds of copper-zinc-tin-sulfur based solar batteries, is characterized in that, are made by the preparation method described in claim 16.
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