CN105633203B - The method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface - Google Patents
The method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface Download PDFInfo
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Abstract
The present invention relates to technical field of solar batteries, specifically disclose a kind of method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, specifically include after copper-zinc-tin-sulfur film material is placed on into quartz tube furnace selenizing or vulcanization, copper-zinc-tin-sulfur film material is placed on electrochemical workstation, only substrate and Mo connection working electrodes；The anhydrous villaumite of 0.001~1M/L and the mixed solution of ionic liquid are prepared, ionic liquid is Choline Chloride and urea in mass ratio 1:0.1~3 mixes；Heat solution, apply electric signal, taken out after 1~600S for the treatment of, electric signal is any one of cyclic voltammetric electric signal, constant pressure electric signal, constant current electric signal, pulse voltage electric signal or pulse current electric signal.The method of the present invention can carry out selective corrosion to copper-zinc-tin-sulfur surface, not only remove the copper selenium secondary phase (Cu on copper-zinc-tin-sulfur film surfacexSe), and the non-uniform phenomenon that chemical etching in the aqueous solution brings to absorbed layer surface corrosion is avoided, it is environment-friendly, it is simple to operate.
Description
Technical field
The invention belongs to technical field of solar batteries, more particularly to a kind of non-aqueous electrochemical etching copper-zinc-tin-sulfur film material
The method for expecting surface.
Background technology
Solar energy is the abundantest energy in numerous regenerative resources, and the global sunshine energy of a hour is equivalent to
The earth energy consumption of a year, significantly larger than wind energy, underground heat, water power, ocean energy, biological energy source equal energy source.Solar energy is in future source of energy knot
Proportion in structure will be increasing, and conservative estimation this proportion can be more than 60% in 2100.Therefore, solar cell research is not
Carry out the important topic of energy development.
Copper-zinc-tin-sulfur (CuZnxSnySz, selenium Se is may also comprise, it is abbreviated as CZTS) it is a kind of derivative of CIGS CIGS
Thing, crystal structure similar to yellow copper structure CIS, abundant raw materials and environmental protection.The absorption coefficient of light of CZTS materials reaches
To 104/ cm, a width of 1.5eV of forbidden band band, photovoltaic optimum bandwidth is more nearly than CIS, and theoretical conversion efficiencies are up to 32.2%.
Therefore, CZTS batteries have extraordinary development prospect, get a good chance of turning into the main flow of following solar cell.
Copper-zinc-tin-sulfur film solar cell is multi-layer film structure, is generally included：Substrate, back electrode, copper zinc tin sulfur absorption layer,
Cushion, Window layer, transparency conducting layer etc., wherein copper zinc tin sulfur absorption layer are the parts of solar cell most critical, are determined
The quality of its performance.Conventional industry is prepared in the technology of copper-zinc-tin-sulfur film solar cell, more using selenizing after preformed layer
Method, the advantage of this method is, equipment requirement is lower and easy large-scale pipeline production.But, this method also easily exists
The dephasign of richness Cu, such as Cu are produced after selenizing on copper-zinc-tin-sulfur film surfacexSe、CuxSn、CuxS、CuxSeS etc..These dephasigns
With low bandwidth high conductivity, the complex centre of the photo-generated carrier pair of battery can be turned into, the performance of serious harm solar cell,
Therefore copper-zinc-tin-sulfur film surface is modified by special method, eliminates richness Cu dephasigns, battery performance can be improved.
Tanaka of Japanese Saga University etc. (Journal of Chromatography A, 1107 (2006) 290-293)
Copper-zinc-tin-sulfur preformed layer is prepared using vapour deposition method, the key problem of research is exactly find tri- kinds of metallic elements of Cu-Zn-Sn optimal
Proportioning, its result display CZTS films are in a kind of poor Cu (Cu/Zn+Sn<1) richness Zn (Zn/Sn>1) during proportioning, by XRD
Harmful secondary phase constituent is effectively reduced during test finds copper-zinc-tin-sulfur film.This mode mainly by the adjustment of preparation technology come
Harmful copper-rich phase is reduced, technical difficulty is high, and effect is difficult to obtain.
Shafaat Ahmed of IBM Corporation of the U.S. etc. (Advanced Energy Materials, (2011) n/a-n/a)
Electro-deposition Cu/Zn/Sn and Cu/Sn/Zn preformed layers, annealing recrystallization is carried out by this preformed layer stage by stage in aqueous.The
The process annealing in one stage is in pure N2Inert atmosphere under carry out, 210-350 DEG C of temperature, formed CuZn, CuSn alloy；Second-order
Alloy film is warming up to more than 550 DEG C by section, with the S reaction generation CZTS polycrystalline films for adding.They anneal by hot stage
The optimal control of temperature eliminates Cu2S, SnS and Cu2Harmful secondary phase such as SnS, makes CZTS film things mutually pure.This skill
Art can play the purpose for eliminating the harmful secondary phase of copper-zinc-tin-sulfur film, but the cost of technology is at a relatively high, and technique controlling difficulty
Coefficient is high, is unfavorable for industrialization promotion.
Patent 102496659A discloses a kind of preparation method of copper-zinc-tin-sulfur film material, the gold that the technology is prepared
Category preformed layer carries out the high temperature anneal first in protective atmosphere under sulfur-bearing atmosphere, is subsequently placed in alkaline KCN solution
Row etching processing.KCN solution has certain etching effect, but can cause remaining adverse reaction, it is necessary to precise control condition.Adopt
Perform etching in this way it is simple to operate, but KCN is in itself extremely toxic substance, large-scale industry application brings environmental protection to ask
Topic.
The content of the invention
The main object of the present invention is directed to the deficiencies in the prior art, and serious, the relatively costly problem of environmental pollution,
A kind of method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface is provided.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is as follows：
The method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, comprises the following steps：
Step (1)：Copper-zinc-tin-sulfur film material selenizing or selenizing in constant-temperature tubular annealing furnace, are then placed within electrochemistry
Work station, only substrate and Mo back electrodes connect working electrode；Then 1~2min is soaked in absolute ethyl alcohol, surface particles are removed
Impurity, high pure nitrogen drying；
Step (2)：Processing solution is prepared, the processing solution is the anhydrous villaumite of 0.001~1M/L and mixing for ionic liquid
Solution is closed, the ionic liquid is Choline Chloride and urea in mass ratio 1:0.1~3 mixes；The villaumite be selected from sodium chloride,
The mixture of any one or more of potassium chloride, magnesium chloride, zinc chloride or copper chloride；
Step (3)：The copper-zinc-tin-sulfur film material of step (1) treatment is put into processing solution obtained in step (2), is heated
Processing solution obtained in step (2), apply electric signal, treatment 1~600S after take out the copper-zinc-tin-sulfur film material, spend from
Sub- water is rinsed, high pure nitrogen drying, and the electric signal is cyclic voltammetric electric signal, constant pressure electric signal, constant current electric signal, pulse electricity
Any one of piezoelectric signal or pulse current electric signal.
As area of solar cell, not yet it is related to electrochemically process copper-zinc-tin-sulfur solar battery obsorbing layer
The report of the method for film.It is molten that the present inventor obtains electrochemical treatments of the invention by long term test, by screening
Liquid, the copper-zinc-tin-sulfur film of copper-zinc-tin-sulfur solar cell is processed by electrochemical method, can be thin with selective etch copper-zinc-tin-sulfur
The high connductivity copper-rich phase on film surface, it is thus also avoided that in the aqueous solution chemical method etching absorbed layer surface corrosion is brought it is uneven
Phenomenon, while environmental sound, process is simple, high recycling rate, low cost, process can be with precise control.Side of the invention
Method, the structure of copper-zinc-tin-sulfur film material includes substrate, Mo and copper-zinc-tin-sulfur film layer successively.Substrate both can be rigid base
Bottom, such as soda-lime glass, or flexible substrates, such as polyimides, stainless steel, molybdenum foil, aluminium foil, copper foil or titanium foil sheet
Deng.The deposition process of copper-zinc-tin-sulfur film can be sputter, electroplate, spin coating, altogether evaporation and Hydrothermal Synthesiss etc..
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, the villaumite it is dense
It is 0.001~0.3M/L to spend.The selection of villaumite consumption, not only needs to improve the electric conductivity of processing solution as much as possible, beneficial to electricity
Mass transfer in chemical process, but also to avoid electrochemical treatment process cationic that doping is caused to battery obsorbing layer.
The method that copper-zinc-tin-sulfur film material surface is etched as further preferred, foregoing non-aqueous electrochemical, the chlorine
The concentration of salt is 0.2M/L.
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, the Choline Chloride
It is 1 with the mass ratio of urea:2.By screening the mass ratio of Choline Chloride and urea, can cause that processing solution of the invention is same
When possess the advantage of electric conductivity and viscosity.
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, in step (3), plus
Heat treatment solution is to 60 DEG C~80 DEG C.Under the state of temperature, processing solution is in optimum activity.
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, the electric signal choosing
From it is following any one：
A. electric signal is cyclic voltammetric electric signal, and the voltage range of the cyclic voltammetric electric signal is -1~1V；
B. the electric signal is constant pressure electric signal, and the voltage range of the constant pressure electric signal is 0.01~1.5V；
C. the electric signal is constant current electric signal, and the current range of the constant current electric signal is 0.01~100mA/cm2；
D. the electric signal is pulse voltage electric signal, and the voltage range of the pulse voltage electric signal is 0.1~1.5V,
Burst length is 5ms, and interval time is 50ms；
E. the electric signal is pulse current electric signal, the current range of the pulse current electric signal for 0.01~
200mA/cm2, the burst length is 5ms, and interval time is 50ms.
The present invention is by the selection to electric signal (including voltage, electric current) and between working time, burst length and time
Every selection, selective etch effectively both was carried out to copper-zinc-tin-sulfur film, at the same turn avoid chemical method excessive corrosion and
The thin film grain-boundary defect for causing increases.
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, the copper-zinc-tin-sulfur
The substrate of film is selected from any one of soda-lime glass, polyimides, stainless steel, molybdenum foil, aluminium foil, copper foil or titanium foil sheet.
Preferably, the method that foregoing non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, the electrochemistry work
The mode of operation stood of work is three-electrode system, including working electrode, reference electrode and gauze platinum electrode, and described reference electrode is Pt
Electrode, potential relative standard's hydrogen potential of the reference electrode is -0.72V.
The method that copper-zinc-tin-sulfur film material surface is etched as further preferred, foregoing non-aqueous electrochemical, the chlorine
Salt is selected from any one of sodium chloride or potassium chloride.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the method that non-aqueous electrochemical of the invention etches copper-zinc-tin-sulfur film material surface, can be with selective etch copper
The high connductivity copper-rich phase on zinc-tin-sulfur film surface, contributes to the optimization of solar cell device interfaces characteristic, excellent beneficial to being formed
Pn-junction characteristic.
2nd, the method that non-aqueous electrochemical of the invention etches copper-zinc-tin-sulfur film material surface, the non-aqueous electrochemical of use
Processing solution is the ionic liquid solution system of anhydrous villaumite, Choline Chloride and urea composition, and solution temperature is low, good conductivity, electricity
Chemical window is wide, and more than 2.5V, steam is forced down, all more stable in the environment of air and water, the alkaline KCN with prior art
Liquid system compares, and overcomes that etchant solution system is harmful and shortcoming not environmentally, environment-friendly；Avoid the aqueous solution
The non-uniform phenomenon that middle chemical method etching is brought to absorbed layer surface corrosion.
3rd, the method that non-aqueous electrochemical of the invention etches copper-zinc-tin-sulfur film material surface, low production cost, treatment side
Method is simple and is easy to precise control, can use various electric signals, such as cyclic voltammetric, constant pressure, constant current, pulse voltage or pulse electricity
Stream etc., the process time needed for electrochemical etching process is short, is conducive to industrialization promotion.
Brief description of the drawings
Fig. 1 is the equipment schematic diagram that non-aqueous electrochemical of the invention etches copper-zinc-tin-sulfur film material surface method；
Fig. 2 is the copper-zinc-tin-sulfur film surface electron microscope after selenizing furnace annealing in embodiment 1；
Fig. 3 is the copper-zinc-tin-sulfur film surface electron microscope after non-aqueous electrochemical etching in embodiment 1；
Fig. 4 is the copper-zinc-tin-sulfur film surface electron microscope after non-aqueous electrochemical etching in embodiment 2；
Fig. 5 is the copper-zinc-tin-sulfur film surface electron microscope after non-aqueous electrochemical etching in embodiment 3.
Wherein, in Fig. 1,1- electrochemical workstations, 2- copper-zinc-tin-sulfur films, 3- substrates, 4-Mo layers, 5- reference electrodes, 6-
Gauze platinum electrode, 7- processing solutions.
Specific embodiment
Foregoing invention content of the invention is described in further detail with reference to specific embodiment.
But this scope for being interpreted as above-mentioned theme of the invention should not be only limitted to following embodiments.On the present invention is not departed from
State in the case of technological thought, according to ordinary skill knowledge and customary means, make various replacements and change, all should include
Within the scope of the invention.
In following examples, as shown in figure 1, the copper-zinc-tin-sulfur film 2 to be processed is connected to electrification by Mo4 and substrate 3
Learn on work station 1, copper-zinc-tin-sulfur film 2 is immersed in processing solution 7, by applying electric signal, copper-zinc-tin-sulfur film 2 is entered
Row etching.Electrochemical workstation 1 takes three electrode mode of operations, includes reference electrode 5 and gauze platinum electrode 6, wherein, reference electricity
Pole 5 can be Pt electrodes, and potential relative standard's hydrogen potential of reference electrode 5 is -0.72V.
The present embodiment of embodiment 1 is non-aqueous electrochemical method etching copper-zinc-tin-sulfur film surface
On soda-lime glass substrate deposit thickness be 1 μm of metal Mo as back electrode, it is heavy using electrochemistry on Mo layers 4
Long-pending method deposit thickness is 1~2 μm of copper-zinc-tin-sulfur film, and the layer film is preformed layer.
Step (1)：The selenizing in constant-temperature tubular annealing furnace of copper-zinc-tin-sulfur film material, is then placed within electrochemical operation
Stand, only substrate 3 and Mo4 back electrodes are connected to the working electrode of electrochemical workstation 1；Then in absolute ethyl alcohol immersion 1~
2min, removes surface particles impurity, high pure nitrogen drying；
Step (2) prepares processing solution 7.It is 1 that anhydrous sodium chloride is dissolved in into mass ratio:2 Choline Chloride and urea is molten
In liquid, concentration of the anhydrous sodium chloride in processing solution 7 is 0.2M/L.
Step (3)：Processing solution 7 is heated to 65 DEG C, then uses constant voltage mode to apply a size constant for 1.2V
Voltage, copper-zinc-tin-sulfur film material is taken out after treatment 200s, is rinsed with deionized water water, high pure nitrogen drying.
As seen in Figure 3, the roughness on the surface of copper-zinc-tin-sulfur film 2 for being obtained after non-aqueous electrochemical etching is changed
Kind, the surface structure for exposing is homogeneous, and crystal property is preferable.Through Raman spectral detections, electrochemical treatments rear film surface is obtained
Secondary phase (such as CuxSe) significantly reduce and even disappear.Compare discovery, the copper zinc of present invention etching with the battery not performed etching
The short-circuit current density of tin sulfur solar energy effectively increases 1~1.5mA/cm2。
The present embodiment of embodiment 2 is non-aqueous electrochemical method etching copper-zinc-tin-sulfur film surface
On soda-lime glass substrate deposit thickness be 1 μm of metal Mo as back electrode, it is heavy using electrochemistry on Mo layers 4
Long-pending method deposit thickness is 1~2 μm of copper-zinc-tin-sulfur film, and the layer film is preformed layer.
Step (1)：The selenizing in constant-temperature tubular annealing furnace of copper-zinc-tin-sulfur film material, is then placed within electrochemical operation
Stand, only substrate 3 and Mo4 back electrodes are connected to the working electrode of electrochemical workstation 1；Then in absolute ethyl alcohol immersion 1~
2min, removes surface particles impurity, high pure nitrogen drying；
Step (2) prepares processing solution 7.It is 1 that anhydrous potassium chloride is dissolved in into mass ratio:3 Choline Chloride and urea is molten
In liquid, concentration of the anhydrous potassium chloride in processing solution 7 is 0.3M/L.
Step (3)：Processing solution 7 is heated to 70 DEG C, it is 25mA/cm then to use constant current mode to apply a size2V's
Constant current, copper-zinc-tin-sulfur film material is taken out after treatment 160s, with deionized water rinsing, high pure nitrogen drying.
As seen in Figure 4, the electrochemical etching surface of copper-zinc-tin-sulfur film 2 is rougher and electric conductivity preferable portion
Point, the surface structure exposed after etching is homogeneous, and crystal property is preferable.Through Raman spectral detections, show thin after electrochemical treatments
Secondary phase (such as Cu on film surfacexSe) significantly reduce and even disappear.Compare discovery, present invention etching with the battery not performed etching
The short-circuit current density of copper-zinc-tin-sulfur solar cell effectively increase 0.5~1mA/cm2。
The present embodiment of embodiment 3 is non-aqueous electrochemical method etching copper-zinc-tin-sulfur film surface
On soda-lime glass substrate deposit thickness be 1 μm of metal Mo as back electrode, it is heavy using electrochemistry on Mo layers 4
Long-pending method deposit thickness is 1~2 μm of copper-zinc-tin-sulfur film, and the layer film is preformed layer.
Step (1)：The selenizing in constant-temperature tubular annealing furnace of copper-zinc-tin-sulfur film material, is then placed within electrochemical operation
Stand, only substrate 3 and Mo4 back electrodes are connected to the working electrode of electrochemical workstation 1；Then in absolute ethyl alcohol immersion 1~
2min, removes surface particles impurity, high pure nitrogen drying；
Step (2) prepares processing solution 7.It is 1 that anhydrous magnesium chloride is dissolved in into mass ratio:2.5 Choline Chloride and urea
In solution, concentration of the anhydrous magnesium chloride in processing solution 7 is 1M/L.
Step (3)：Processing solution 7 is heated to 70 DEG C, a pulse voltage signal is then applied using pulse voltage pattern,
Voltage is 1V, and the burst length is 5ms, and interval time is 50ms, and copper-zinc-tin-sulfur film material is taken out after process time 240s, is spent
Ionized water is rinsed, high pure nitrogen drying.
As seen in Figure 5, the surface structure on the surface of copper-zinc-tin-sulfur film 2 for being obtained after electrochemical etching is homogeneous, and
Crystal property is preferable.Through Raman spectral detections, secondary phase (such as Cu on electrochemical treatments rear film surface is obtainedxSe) substantially subtract
It is few even to disappear.Compare discovery, the short circuit current of the copper-zinc-tin-sulfur solar cell of present invention etching with the battery not performed etching
Density effectively increases 0.5~1.2mA/cm2。
4~embodiment of embodiment 14,4~embodiment of embodiment 14 is that non-aqueous electrochemical method etches copper-zinc-tin-sulfur film table
The step of face (2), prepares processing solution, and step (3) applies electric signal, and other steps are same as Example 1.Specifically it is shown in Table 1.
4~the embodiment of embodiment 14 of table 1.
Claims (9)
1. the method that non-aqueous electrochemical etches copper-zinc-tin-sulfur film material surface, it is characterised in that comprise the following steps：
Step (1)：Copper-zinc-tin-sulfur film material selenizing or vulcanization in constant-temperature tubular annealing furnace, are then placed within electrochemical operation
Stand, only substrate and Mo back electrodes connection working electrode；Then 1~2min is soaked in absolute ethyl alcohol, surface particles impurity is removed,
High pure nitrogen is dried up；
Step (2)：Processing solution is prepared, the processing solution is that the mixing of the anhydrous villaumite and ionic liquid of 0.001~1M/L is molten
Liquid, the ionic liquid is Choline Chloride and urea in mass ratio 1:0.1~3 mixes；The villaumite is selected from sodium chloride, chlorination
The mixture of any one or more of potassium, magnesium chloride, zinc chloride or copper chloride；
Step (3)：The copper-zinc-tin-sulfur film material of step (1) treatment is put into processing solution, heating stepses obtained in step (2)
(2) processing solution obtained in, applies electric signal, and the copper-zinc-tin-sulfur film material is taken out after 1~600S for the treatment of, uses deionized water
Rinse, high pure nitrogen drying, the electric signal is cyclic voltammetric electric signal, constant pressure electric signal, constant current electric signal, pulse voltage electricity
Any one of signal or pulse current electric signal.
2. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The concentration of the villaumite is 0.001~0.3M/L.
3. the method that non-aqueous electrochemical according to claim 2 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The concentration of the villaumite is 0.2M/L.
4. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The Choline Chloride is 1 with the mass ratio of urea:2.
5. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
In step (3), heat solution to 60 DEG C~80 DEG C.
6. the method that the non-aqueous electrochemical according to any one of Claims 1 to 5 etches copper-zinc-tin-sulfur film material surface, its
Be characterised by, the electric signal be selected from it is following any one：
A. electric signal is cyclic voltammetric electric signal, and the voltage range of the cyclic voltammetric electric signal is -1~1V；
B. the electric signal is constant pressure electric signal, and the voltage range of the constant pressure electric signal is 0.01~1.5V；
C. the electric signal is constant current electric signal, and the current range of the constant current electric signal is 0.01~100mA/cm2；
D. the electric signal is pulse voltage electric signal, and the voltage range of the pulse voltage electric signal is 0.1~1.5V, pulse
Time is 5ms, and interval time is 50ms；
E. the electric signal is pulse current electric signal, and the current range of the pulse current electric signal is 0.01~200mA/
cm2, the burst length is 5ms, and interval time is 50ms.
7. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The substrate of the copper-zinc-tin-sulfur film is selected from soda-lime glass, polyimides, stainless steel, molybdenum foil, aluminium foil, copper foil or titanium foil
Any one of piece.
8. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The mode of operation of the electrochemical workstation is three-electrode system, including working electrode, reference electrode and gauze platinum electrode are described
Reference electrode is Pt electrodes, and potential relative standard's hydrogen potential of the reference electrode is -0.72V.
9. the method that non-aqueous electrochemical according to claim 1 etches copper-zinc-tin-sulfur film material surface, it is characterised in that
The villaumite is selected from any one of sodium chloride or potassium chloride.
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| CN102492972A (en) * | 2011-12-12 | 2012-06-13 | 云南师范大学 | Electrochemical preparation process of Cu2ZnSnS4 film |
| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
| CN103060861A (en) * | 2013-02-03 | 2013-04-24 | 电子科技大学 | Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition |
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| CN102741458A (en) * | 2009-09-08 | 2012-10-17 | 西安大略大学 | Electrochemical method of producing copper indium gallium diselenide (cigs) solar cells |
| CN102492972A (en) * | 2011-12-12 | 2012-06-13 | 云南师范大学 | Electrochemical preparation process of Cu2ZnSnS4 film |
| CN103060861A (en) * | 2013-02-03 | 2013-04-24 | 电子科技大学 | Method for preparing copper-zinc-tin-sulfur film through co-electrodeposition |
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