CN102877101B - Method for preparing solar cell buffer layer ZnS film through electro-deposition by taking CuInSe2 film as base - Google Patents
Method for preparing solar cell buffer layer ZnS film through electro-deposition by taking CuInSe2 film as base Download PDFInfo
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- CN102877101B CN102877101B CN201210379774.0A CN201210379774A CN102877101B CN 102877101 B CN102877101 B CN 102877101B CN 201210379774 A CN201210379774 A CN 201210379774A CN 102877101 B CN102877101 B CN 102877101B
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Abstract
The invention relates to a method for preparing a solar cell buffer layer ZnS film through electro-deposition by taking a CuInSe2 film as a base, and aims to solve the problem of low transmittance of a solar cell buffer layer ZnS film prepared by an existing method. The method includes the steps: firstly, pre-treating conductive glass; secondly, preparing the CuInSe2 film through constant-voltage electro-deposition by a two-electrode system; thirdly, performing heat treatment for the CuInSe2 film; fourthly, preparing the ZnS film through constant-voltage electro-deposition by the two-electrode system; and fifthly, performing heat treatment for the ZnS film. The transmittance of the solar cell buffer layer ZnS film prepared by the method reaches 80%-90%, production cost is greatly saved, and the method has the advantages of high deposition speed, simplicity in operation, safety and the like, is quite suitable for large-scale preparation of ZnS films and is applied to the field of solar cells.
Description
Technical field
The present invention relates to a kind of method preparing solar cell buffer layer ZnS film.
Background technology
Galvanic deposit is a kind of fairly simple and cheap deposition technique, and application surface is extremely wide, can form large-scale production.Although the film crystalline quality of deposition growth is slightly poorer than some other technology, its productivity in all deposition techniques is the highest, and can realize extensive deposition and deposit at comparatively complex surface.In semiconductor thin-film solar cell, galvanic deposit can be passed through growth technique (as application potential energy, pH value, electrolysis temperature etc.) and change the material behavior such as band gap and lattice parameter relatively easily, thus has some superiority preparing on overlapping thin film solar battery.Existing at CuInSe
2method ZnS film preparing by film is sputtering method, method of evaporation etc. mostly, what traditional copper, indium and selenium film solar cell buffer layer was multiplex greatly be CdS film but due to CdS film poisonous, can to environment, simultaneously because energy gap value (2.42eV) that CdS film is lower can limit the short wave response of solar cell, improve short-circuit current and the open circuit voltage of battery.ZnS film is prepared in alkaline system at present mainly in pH >=7 or neutral system galvanic deposit, the ZnS film transmission rate lower (50% ~ 60%) prepared in alkalescence or neutral system.
Summary of the invention
The object of the invention is to prepare the low problem of solar cell buffer layer ZnS film transmission rate to solve existing method, and provide with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit.
Of the present invention with CuInSe
2film is that the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit is carried out according to following steps:
One, the pre-treatment of conductive glass
Pre-treatment is carried out to conductive glass, stand-by;
Two, CuInSe is prepared in galvanic deposit
2film
Adopt graphite as anode, using the conductive glass after step one pre-treatment as working electrode, anode and working electrode are put into CuInSe
2carry out constant voltage galvanic deposit in electrodeposit liquid, after deposition, take out working electrode, with distilled water cleaning 5 ~ 10 times, and after drying up, obtain CuInSe
2film;
Three, CuInSe
2the thermal treatment of film
The CuInSe that step 2 is obtained
2film is 300 ~ 400 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 30 ~ 40min;
Four, ZnS film is prepared in galvanic deposit
Adopt graphite as anode, with the CuInSe after step 3 thermal treatment
2anode and working electrode, as working electrode, are put into ZnS electrodeposit liquid and are carried out constant voltage galvanic deposit by film, after deposition, take out working electrode distilled water flushing 3 ~ 5 times, and after drying up, obtain ZnS film;
Five, the thermal treatment of ZnS film
ZnS film step 4 obtained is 50 ~ 70 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely complete with CuInSe
2film is that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Wherein, the CuInSe described in step 2
2electrodeposit liquid is by the CuSO of 1 ~ 1.5mmol/L
45H
2the In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2form with the Trisodium Citrate of 0.1 ~ 0.3mol/L, CuInSe
2the pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in step 4 is by the ZnSO of 0.1 ~ 0.2mol/L
4, 0.2 ~ 0.3mol/L NaS
2o
3form with the Trisodium Citrate of 0.1 ~ 0.2mol/L, the pH value of ZnS electrodeposit liquid is the temperature of 3 ~ 4, ZnS electrodeposit liquid is 50 DEG C ~ 60 DEG C;
Constant voltage electrodeposition condition described in step 4 is: voltage is 2 ~ 3V, and current density is 1 ~ 2mA/cm
2, depositing time is 4 ~ 6min.
The present invention comprises following beneficial effect:
The CuInSe that the present invention adopts the method for galvanic deposit preparing
2depositing solar cell buffer layer ZnS film on film, in high spot reviews galvanic deposit, processing condition are on the impact of preparation ZnS film, and comprise the impact on film performance of its electrolyte ph, current density and depositing time, the present invention is with CuInSe
2film is that the transmitance that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit reaches 80% ~ 90%, and for obtaining high-level efficiency, the flexible substrate film solar cell of low cost opens up new way.
The present invention uses electro-deposition method on copper, indium and selenium film, prepare solar cell buffer layer ZnS film and not only greatly saves production cost, but also has the features such as sedimentation rate is fast, simple to operate, safe, is applicable to very much extensive preparation ZnS film.
ZnS film is nontoxic and have higher energy gap value (about 3.7eV), not only makes to combine between absorption layer and Window layer tightr, plays structure shock absorption simultaneously, reduces the effect of lattice mismatch.In addition in the past at CuInSe
2the methods such as the large multiplex magnetron sputtering of ZnS buffer layer, vacuum-evaporation prepared by film to prepare, simultaneously because sputtering method, method of evaporation have expensive cost and be difficult to accomplish scale operation, and the present invention selects electro-deposition method at CuInSe
2its very thin thickness of ZnS film prepared by film, structure is very fine and close, greatly reduces production cost simultaneously, can accomplish scale operation.
The scope of the electrolyte ph that existing galvanic deposit ZnS film uses is mostly=7 or the system of >7, be neutrality or alkaline system, the ZnS film transmission rate lower (50% ~ 60%) prepared.The present invention is the galvanic deposit carried out in acid (pH<7) system, is conducive to the generation of S, and is converted into S in this individual system under the effect of electrolysis
2+, thus abundant sulphur source is provided, promote deposition and the growth of film, the ZnS film of the 50 ~ 100nm that can prepare, structure is very fine and close, and transmitance reaches 80% ~ 90%, serves excellent translucent effect.
And existing electro-deposition method is prepared ZnS film and is not applied to solar cell buffer layer, has not both adopted electro-deposition method at CuInSe
2film deposits ZnS film, and adopt galvanic deposit to prepare ZnS film and also seldom study at acid system, the present invention obtains at CuInSe through experimental study
2film deposits the optimum process condition of ZnS film.
The present invention adopts cathodic reduction sedimentation mechanism at CuInSe
2film deposits ZnS film, specific as follows: S
2o
3 2-first at H
+effect under decomposite the S simple substance scope of pH value control <7 of electrolytic solution (so during deposition of the present invention), then, the S simple substance decomposited is diffused on negative electrode under the effect of concentration gradient, obtain electronics to be reduced, because this reactions steps is comparatively slow, become the rate-determining steps of whole electrochemical reaction speed.
S
2O
3 2-+6H
++4e→2S+3H
2O （1）
S+e→S
2-（2）
Finally be positioned at the Zn near pole plate
2+with the S be reduced
2-there is combination reaction and generate product ZnS.
Zn
2++S
2-→ZnS （3）
Accompanying drawing explanation
Fig. 1 is with CuInSe
2film is the afm image that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Fig. 2 is with CuInSe
2film is the section afm image that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Fig. 3 is with CuInSe
2film is the thickness map that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Fig. 4 is with CuInSe
2film is pH value and the transmittance curve integral area figure that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Fig. 5 is with CuInSe
2film is the current density transmittance curve integral area graph of a relation that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Fig. 6 is with CuInSe
2film is that the depositing time of solar cell buffer layer ZnS film and the wavelength transmittance curve integral area graph of a relation of film are prepared in matrix galvanic deposit;
Fig. 7 is with CuInSe
2film is wavelength-transmittance curve figure that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit.
Embodiment
Below in conjunction with the embodiment of the best, the invention will be further described, but protection scope of the present invention is not limited in following examples.
Embodiment one: present embodiment with CuInSe
2film is that the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit is carried out according to following steps:
One, the pre-treatment of conductive glass
Pre-treatment is carried out to conductive glass, stand-by;
Two, CuInSe is prepared in galvanic deposit
2film
Adopt graphite as anode, using the conductive glass after step one pre-treatment as working electrode, anode and working electrode are put into CuInSe
2carry out constant voltage galvanic deposit in electrodeposit liquid, after deposition, take out working electrode, with distilled water cleaning 5 ~ 10 times, and after drying up, obtain CuInSe
2film;
Three, CuInSe
2the thermal treatment of film
The CuInSe that step 2 is obtained
2film is 300 ~ 400 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 30 ~ 40min;
Four, ZnS film is prepared in galvanic deposit
Adopt graphite as anode, with the CuInSe after step 3 thermal treatment
2anode and working electrode, as working electrode, are put into ZnS electrodeposit liquid and are carried out constant voltage galvanic deposit by film, after deposition, take out working electrode distilled water flushing 3 ~ 5 times, and after drying up, obtain ZnS film;
Five, the thermal treatment of ZnS film
ZnS film step 4 obtained is 50 ~ 70 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely complete with CuInSe
2film is that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Wherein, the CuInSe described in step 2
2electrodeposit liquid is by the CuSO of 1 ~ 1.5mmol/L
45H
2the In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2form with the Trisodium Citrate of 0.1 ~ 0.3mol/L, CuInSe
2the pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in step 4 is by the ZnSO of 0.1 ~ 0.2mol/L
4, 0.2 ~ 0.3mol/L NaS
2o
3form with the Trisodium Citrate of 0.1 ~ 0.2mol/L, the pH value of ZnS electrodeposit liquid is the temperature of 3 ~ 4, ZnS electrodeposit liquid is 50 DEG C ~ 60 DEG C;
Constant voltage electrodeposition condition described in step 4 is: voltage is 2 ~ 3V, and current density is 1 ~ 2mA/cm
2, depositing time is 4 ~ 6min.
The CuInSe that present embodiment adopts the method for galvanic deposit preparing
2depositing solar cell buffer layer ZnS film on film, in high spot reviews galvanic deposit, processing condition are on the impact of preparation ZnS film, and comprise the impact on film performance of its electrolyte ph, current density and depositing time, present embodiment is with CuInSe
2film is that the transmitance that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit reaches 80% ~ 90%, and for obtaining high-level efficiency, the flexible substrate film solar cell of low cost opens up new way.
Present embodiment uses electro-deposition method on copper, indium and selenium film, to prepare solar cell buffer layer ZnS film not only greatly save production cost, but also has the features such as sedimentation rate is fast, simple to operate, safe, is applicable to very much preparing ZnS film on a large scale.
ZnS film is nontoxic and have higher energy gap value (about 3.7eV) and not only make to combine between absorption layer and Window layer tightr, plays structure shock absorption simultaneously, reduces the effect of lattice mismatch.In addition in the past at CuInSe
2the methods such as the large multiplex magnetron sputtering of ZnS buffer layer, vacuum-evaporation prepared by film to prepare, simultaneously because sputtering method, method of evaporation have expensive cost and be difficult to accomplish scale operation, and present embodiment selects electro-deposition method at CuInSe
2its very thin thickness of ZnS film prepared by film, structure is very fine and close, greatly reduces production cost simultaneously, can accomplish scale operation.
The scope of the electrolyte ph that existing galvanic deposit ZnS film uses is mostly=7 or the system of >7, be neutrality or alkaline system, the ZnS film transmission rate lower (50% ~ 60%) prepared.The present invention is the galvanic deposit carried out in acid (pH<7) system, is conducive to the generation of S, and is converted into S in this individual system under the effect of electrolysis
2+, thus abundant sulphur source is provided, promote deposition and the growth of film, the ZnS film of the 50 ~ 100nm that can prepare, structure is very fine and close, and transmitance reaches 80% ~ 90%, serves excellent translucent effect.
And existing electro-deposition method is prepared ZnS film and is not applied to solar cell buffer layer, has not both adopted electro-deposition method at CuInSe
2film deposits ZnS film, and adopt galvanic deposit to prepare ZnS film and also seldom study at acid system, present embodiment obtains at CuInSe through experimental study
2film deposits the optimum process condition of ZnS film.
Present embodiment adopts cathodic reduction sedimentation mechanism at CuInSe
2film deposits ZnS film, specific as follows: S
2o
3 2-first at H
+effect under decomposite the S simple substance scope of the pH value control <7 of electrolytic solution (so during the deposition of present embodiment), then, the S simple substance decomposited is diffused on negative electrode under the effect of concentration gradient, obtain electronics to be reduced, because this reactions steps is comparatively slow, become the rate-determining steps of whole electrochemical reaction speed.
S
2O
3 2-+6H
++4e→2S+3H
2O （1）
S+e→S
2-（2）
Finally be positioned at the Zn near substrate
2+with the S be reduced
2-there is combination reaction and generate product ZnS.
Zn
2++S
2-→ZnS （3）
Embodiment two: present embodiment and embodiment one unlike: the conductive glass described in step one is FTO conductive glass.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the pre-treatment step described in step one is: successively with washing powder clean conductive glass 1 ~ 2 time, distilled water clean conductive glass 5 ~ 10 times, acetone clean conductive glass 1 ~ 2 time, distilled water clean conductive glass 5 ~ 10 times, washes of absolute alcohol conductive glass 1 ~ 2 time and distilled water cleans conductive glass 5 ~ 10 times, then dry up.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are unlike CuInSe described in step 2
2the pH value of electrodeposit liquid and the ZnS electrodeposit liquid described in step 4 is all be the H of 80% with mass percentage
2sO
4solution carry out regulating.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four are unlike CuInSe described in step 2
2the pH value of electrodeposit liquid is 2.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the constant voltage electrodeposition condition described in step 2 is: voltage is 1.2V, and depositing time is 60min.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: the pH value of the ZnS electrodeposit liquid described in step 4 is 3.5.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: the temperature of the ZnS electrodeposit liquid described in step 4 is 60 DEG C.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: the constant voltage electrodeposition condition described in step 4 is: voltage is 2.5V, and current density is 1.5mA/cm
2, depositing time is 6min.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: the temperature described in step 5 is 300 DEG C.Other is identical with one of embodiment one to nine.
By following verification experimental verification beneficial effect of the present invention:
This test with CuInSe
2film is that the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit is carried out according to following steps:
One, the pre-treatment of conductive glass
Select FTO conductive glass as the body material of galvanic deposit ZnS film, pre-treatment is carried out to FTO conductive glass, wherein, pre-treatment step is: clean FTO conductive glass 1 time with washing powder cleaning FTO conductive glass 1 time → distillation washing FTO conductive glass 8 times → acetone → distill washing FTO conductive glass 8 times → washes of absolute alcohol FTO conductive glass 1 time → distillation washing FTO conductive glass 8 times, dry up stand-by after pre-treatment by FTO conductive glass;
Two, the preparation of electrolytic solution
A.CuInSe
2the preparation of electrodeposit liquid
Get the CuSO of 1mmol/L
45H
2the In of O, 9mmol/L
2(SO
4)
3, 4mmol/L SeO
2mix with the Trisodium Citrate of 0.1mol/L and be mixed with CuInSe
2electrodeposit liquid is the H of 80% with mass percentage
2sO
4regulate CuInSe
2electrodeposit liquid pH value to 2;
The preparation of b.ZnS electrodeposit liquid
Take the ZnSO of 0.1mol/L
4, the NaS of 0.2mol/L
2o
3adding a certain amount of distilled water respectively with the Trisodium Citrate of 0.1mol/L makes medicine all dissolve, and by the pH value to 3.5 of vitriol oil regulator solution, regulates the process of pH to be carry out under the condition stirred, is kept by the solution configured and be ready for galvanic deposit.
Three, CuInSe is prepared in galvanic deposit
2film
CuInSe is prepared in galvanic deposit
2film adopts two electrode system constant voltage galvanic deposit, and using graphite as anode, electrode, as negative electrode (working electrode), is put into the CuInSe of step 2 preparation by the FTO conductive glass after step one pre-treatment
2electrodeposit reaction is carried out in electrodeposit liquid; Wherein, deposition voltage is 1.2V, and electrodeposition time is 60min, takes out negative electrode (working electrode) and cleans with distilled water and dry up, obtain CuInSe after having deposited
2film;
Four, CuInSe
2the thermal treatment of film
The CuInSe that step 3 is obtained
2film is 300 DEG C, N in temperature
2thermal treatment under the condition of protection, heat treatment time is 30min;
Five, ZnS film is prepared in galvanic deposit
Galvanic deposit is prepared ZnS film and is adopted two electrode systems to carry out Constant Electric Current deposition, using graphite as anode, and the CuInSe after step 4 thermal treatment
2film is as negative electrode (working electrode), the ZnS electrodeposit liquid that step 2 is prepared is put into thermostat water bath to carry out after heating reaches 60 DEG C, electrode being put into electrolytic solution and carrying out electrodeposit reaction, wherein, in electrodeposition process, voltage is 2.5V, and current density is 1.5mA/cm
2, the temperature of electrolytic solution is 60 DEG C, and electrodeposition time is 6min, takes out the electrolytic solution that the clean film surface of negative electrode (working electrode) distilled water flushing is residual, then dry up with blower, obtain ZnS film after having deposited;
Six, the thermal treatment of ZnS film
ZnS film step 5 galvanic deposit obtained is at temperature 300 DEG C, N
2thermal treatment under the condition of protection, heat treatment time is 1h, after cooling to room temperature with the furnace, namely completes with CuInSe after thermal treatment
2film is that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit.
This test is with CuInSe
2film be the three-dimensional AFM figure of the solar cell buffer layer ZnS film for preparing of matrix galvanic deposit as shown in Figure 1, film is evenly distributed compact structure as seen from Figure 1, distributes in spherical particle.
Fig. 2 is with CuInSe
2film is the section afm image of the solar cell buffer layer ZnS film that matrix galvanic deposit prepares, and as can be seen from the figure ZnS film is very thin, and Fig. 3 is with CuInSe
2film is the thickness map of the solar cell buffer layer ZnS film that matrix galvanic deposit prepares, as can be seen from the figure, the thickness of ZnS film is represented between two arrows, its mean thickness fluctuates near 83.90nm, the effect of structure buffering can be played completely, be suitable as very much the buffer layer of solar cell.
By analyzing the galvanic deposit parameter of this test, investigate different parameters to the impact of ZnS film transmission rate, specific as follows:
1) pH value is on the impact of ZnS film transmission rate
By changing the pH value of the ZnS electrodeposit liquid in this testing sequence five, other Parameter Conditions is constant, then ZnS thin-film electro deposition is carried out according to the method for this test, investigate pH value to the impact of ZnS film transmission rate, result as shown in Figure 4, Fig. 4 is that pH value is respectively 3.0, 3.25, 3.5, the transmittance curve integral area figure of film when 3.75 and 4.0, as can be seen from the figure originally the transmitance of film increases along with the increase of pH value, when pH value is 3.5, the transmittance curve integral area of film reaches maximum, when pH value is greater than 3.5, transmitance declines on the contrary, because the excess deposition of S simple substance causes film transmission rate to reduce when pH value is lower, excessive Zn simple substance is contained in film when pH value is higher, therefore the present invention selects the pH value of galvanic deposit to be 3.5 as optimal ph.
2) current density is on the impact of ZnS film transmission rate
Prepare the current density of ZnS film by changing this testing sequence five galvanic deposit, other Parameter Conditions is constant, then carries out ZnS thin-film electro deposition according to the method for this test, and investigate current density to the impact of ZnS film transmission rate, result as shown in Figure 5.
Fig. 5 is the wavelength transmittance curve integral area graph of a relation of ZnS film under different current density, and determining current density in test is respectively 1.5mA/cm
2, 2.0mA/cm
2, 2.5mA/cm
2and 3.0mA/cm
2time ZnS film transmission rate, as can be seen from Figure 5 the through performance of the increase film of current density reduces gradually, and wherein current density is 1.5mA/cm
2film transmission rate the highest, reach 80% ~ 90% in UV-visible region, and current density is 3.0mA/cm
2film transmission rate minimum less than 10%, therefore select current density be 1.5mA/cm
2be used as the optimum current density of testing, now the transmitance of film in visible region is 80% ~ 90%.
3) depositing time is on the impact of ZnS film transmission rate
Prepare the depositing time of ZnS film by changing this testing sequence five galvanic deposit, other Parameter Conditions is constant, then carries out ZnS thin-film electro deposition according to the method for this test, and investigate depositing time to the impact of ZnS film transmission rate, result as shown in Figure 5.
Fig. 6 is the wavelength transmittance curve integral area graph of a relation of ZnS film under different depositing time, the transmittance curve that depositing time is respectively the ZnS film under 6min, 8min and 10min is determined in test, as can be seen from Figure 6 the transmitance of film reduces gradually along with the increase of depositing time, wherein when deposited between when being 6min the transmitance of film maximum, reach more than 83% in visible region.
From above-mentioned test, the optimum process condition of galvanic deposit ZnS film is: pH value selects 3.5; Current density selects 1.5mA/cm
2; Depositing time selects 6min; Depositing temperature selects 60 DEG C; Thermal treatment temp is 300 DEG C.
As shown in Figure 7, as shown in Figure 7, ZnS film increases in the transmitance in ultraviolet-visible district the wavelength transmittance curve collection of illustrative plates of the ZnS film that this test obtains gradually, tends to be steady near 700nm, reaches 80% ~ 90% in the transmitance of visible region.
Claims (6)
1. with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that with CuInSe
2film is that the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit is carried out according to following steps:
One, the pre-treatment of conductive glass
Pre-treatment is carried out to conductive glass, stand-by;
Two, CuInSe is prepared in galvanic deposit
2film
Adopt graphite as anode, using the conductive glass after step one pre-treatment as working electrode, anode and working electrode are put into CuInSe
2carry out constant voltage galvanic deposit in electrodeposit liquid, after deposition, take out working electrode, with distilled water cleaning 5 ~ 10 times, and after drying up, obtain CuInSe
2film;
Three, CuInSe
2the thermal treatment of film
The CuInSe that step 2 is obtained
2film is 300 ~ 400 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 30 ~ 40min;
Four, ZnS film is prepared in galvanic deposit
Adopt graphite as anode, with the CuInSe after step 3 thermal treatment
2anode and working electrode, as working electrode, are put into ZnS electrodeposit liquid and are carried out constant voltage galvanic deposit by film, after deposition, take out working electrode distilled water flushing 3 ~ 5 times, and after drying up, obtain ZnS film;
Five, the thermal treatment of ZnS film
ZnS film step 4 obtained is 50 ~ 70 DEG C, N in temperature
2under the condition of gas shielded, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely complete with CuInSe
2film is that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit;
Wherein, the CuInSe described in step 2
2electrodeposit liquid is by the CuSO of 1 ~ 1.5mmol/L
45H
2the In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2form with the Trisodium Citrate of 0.1 ~ 0.3mol/L, CuInSe
2the pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in step 4 is by the ZnSO of 0.1 ~ 0.2mol/L
4, 0.2 ~ 0.3mol/L NaS
2o
3form with the Trisodium Citrate of 0.1 ~ 0.2mol/L, the pH value of ZnS electrodeposit liquid is the temperature of 3.5, ZnS electrodeposit liquid is 60 DEG C;
Constant voltage electrodeposition condition described in step 4 is: voltage is 2.5V, and current density is 1.5mA/cm
2, depositing time is 6min;
Conductive glass described in step one is FTO conductive glass.
2. according to claim 1 with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that the pre-treatment step described in step one is: clean conductive glass 5 ~ 10 times with washing powder cleaning conductive glass 1 ~ 2 time, distilled water cleaning conductive glass 5 ~ 10 times, acetone cleaning conductive glass 1 ~ 2 time, distilled water cleaning conductive glass 5 ~ 10 times, washes of absolute alcohol conductive glass 1 ~ 2 time and distilled water successively, then dry up.
3. according to claim 1 with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that the CuInSe described in step 2
2the pH value of electrodeposit liquid and the ZnS electrodeposit liquid described in step 4 is all be the H of 80% with mass percentage
2sO
4solution carry out regulating.
4. according to claim 1 with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that the CuInSe described in step 2
2the pH value of electrodeposit liquid is 2.
5. according to claim 1 with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that the constant voltage electrodeposition condition described in step 2 is: voltage is 1.2V, and depositing time is 60min.
6. according to claim 1 with CuInSe
2film is the method that solar cell buffer layer ZnS film is prepared in matrix galvanic deposit, it is characterized in that the temperature described in step 3 is 300 DEG C.
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| CN105489702A (en) * | 2015-12-16 | 2016-04-13 | 山东建筑大学 | Method for preparing zinc sulfide photoelectric thin film from zinc sulfate |
| CN106591914B (en) * | 2016-12-30 | 2019-01-18 | 哈尔滨理工大学 | A kind of copper indium selenium sulfide thin film solar battery obsorbing layer of electrodeposition process preparation |
| CN109904255B (en) * | 2019-03-19 | 2020-09-29 | 湘潭大学 | Preparation method of Cr-Se co-doped zinc sulfide solar cell buffer layer thin film material |
| CN111697104B (en) * | 2020-06-24 | 2022-05-20 | 哈尔滨理工大学 | Method for preparing copper indium gallium selenide solar cell in full non-vacuum manner |
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