CN102877101A - 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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- CN102877101A CN102877101A CN2012103797740A CN201210379774A CN102877101A CN 102877101 A CN102877101 A CN 102877101A CN 2012103797740 A CN2012103797740 A CN 2012103797740A CN 201210379774 A CN201210379774 A CN 201210379774A CN 102877101 A CN102877101 A CN 102877101A
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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 for 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 that big area deposits and depositing than complex surface.Aspect semiconductor thin-film solar cell, galvanic deposit can change the material behaviors such as band gap and lattice parameter relatively easily by growth technique (as using potential energy, pH value, electrolysis temperature etc.), thereby has some superiority at the preparation overlapping thin film solar battery.Have now at CuInSe
2The method for preparing the ZnS film on the film is sputtering method, method of evaporation etc. mostly, traditional copper, indium and selenium film solar cell buffer layer large multiplex be CdS film but because the CdS film is poisonous, can be to environment, because the lower energy gap value (2.42eV) of CdS film can limit the short wave response of solar cell, improve short-circuit current and the open circuit voltage of battery simultaneously.At present mainly be that alkaline system or neutral system galvanic deposit in pH 〉=7 prepares the ZnS film, the ZnS film transmitance lower (50% ~ 60%) for preparing in alkalescence or neutral system.
Summary of the invention
The objective of the invention is to prepare the low problem of solar cell buffer layer ZnS film transmitance in order to solve existing method, and provide with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film.
Of the present invention with CuInSe
2Film is that the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film is carried out according to following steps:
One, the pre-treatment of conductive glass
Conductive glass is carried out pre-treatment, stand-by;
Two, galvanic deposit prepares CuInSe
2Film
Adopt graphite as anode, as working electrode, anode and working electrode are put into CuInSe with the conductive glass after the step 1 pre-treatment
2Carry out the constant voltage galvanic deposit in the electrodeposit liquid, after the deposition, take out working electrode, clean 5 ~ 10 times with distilled water, and after drying up, namely get CuInSe
2Film;
Three, CuInSe
2The thermal treatment of film
The CuInSe that step 2 is obtained
2Film is 300 ~ 400 ℃, N in temperature
2Under the condition of gas protection, heat-treat 30 ~ 40min;
Four, galvanic deposit prepares the ZnS film
Adopt graphite as anode, with the CuInSe after the step 3 thermal treatment
2Film is as working electrode, anode and working electrode put into the ZnS electrodeposit liquid carry out the constant voltage galvanic deposit, after the deposition, takes out working electrode with distilled water flushing 3 ~ 5 times, and after drying up, namely gets the ZnS film;
Five, the thermal treatment of ZnS film
The ZnS film that step 4 is obtained is 50 ~ 70 ℃, N in temperature
2Under the condition of gas protection, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely finish with CuInSe
2Film is that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Wherein, the CuInSe described in the step 2
2Electrodeposit liquid is the CuSO by 1 ~ 1.5mmol/L
45H
2The In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2Form CuInSe with the Trisodium Citrate of 0.1 ~ 0.3mol/L
2The pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in the step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in the step 4 is the ZnSO by 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 that the temperature of 3 ~ 4, ZnS electrodeposit liquid is 50 ℃ ~ 60 ℃;
Constant voltage electrodeposition condition described in the 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 the film, processing condition comprise its electrolyte ph, current density and depositing time to the impact of film performance to the impact of preparation ZnS film in the high spot reviews galvanic deposit, the present invention is with CuInSe
2Film is that the transmitance that the matrix galvanic deposit prepares solar cell buffer layer ZnS film has reached 80% ~ 90%, for obtain high-level efficiency, the flexible substrate film solar cell is opened up new way cheaply.
The present invention uses electro-deposition method not only greatly to save production cost at copper, indium and selenium film preparation solar cell buffer layer ZnS film, but also has the features such as sedimentation rate is fast, simple to operate, safe, is fit to very much prepare on a large scale the ZnS film.
The ZnS film is nontoxic and have higher energy gap value (about 3.7eV), not only makes between absorption layer and the Window layer in conjunction with tightr, plays simultaneously the structure shock absorption, reduces the effect of lattice mismatch.In addition in the past at CuInSe
2The methods such as the large multiplex magnetron sputtering of preparation ZnS buffer layer, vacuum-evaporation prepare on the film, be difficult to accomplish scale operation owing to sputtering method, method of evaporation have expensive cost simultaneously, and the present invention select electro-deposition method at CuInSe
2Prepare its thickness of ZnS film on the film as thin as a wafer, structure is very fine and close, greatly reduces simultaneously production cost, can accomplish scale operation.
The scope of the electrolyte ph that existing galvanic deposit ZnS film uses mostly is=7 or 7 system, be neutrality or alkaline system, the ZnS film transmitance lower (50% ~ 60%) of preparing.The present invention is the galvanic deposit of carrying out in acid (pH＜7) system, is conducive to the generation of S in this individual system, and is converted into S under the effect of electrolysis
2+, thereby 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 has reached 80% ~ 90%, has played excellent translucent effect.
And existing electro-deposition method prepares the ZnS film and is not applied to the solar cell buffer layer, both do not adopted electro-deposition method at CuInSe
2Deposition ZnS film on the film, and adopt galvanic deposit to prepare the ZnS film at acid system and also seldom study, the present invention has obtained at CuInSe through experimental study
2The optimum process condition of deposition ZnS film on the film.
The present invention adopts the cathodic reduction sedimentation mechanism at CuInSe
2Deposition ZnS film is specific as follows: S on the film
2O
3 2-At first at H
+Effect under decomposite S simple substance (so when deposition of the present invention electrolytic solution pH value control＜7 scope), then, the S simple substance that decomposites is diffused on the negative electrode under the effect of concentration gradient, obtaining electronics is reduced, because this reactions steps is slower, become the control step of whole electrochemical reaction speed.
S
2O
3 2-+6H
++4e→2S+3H
2O （1）
S+e→S
2- （2）
Be positioned at last near the Zn of pole plate
2+With the S that is reduced
2-Combination reaction occurs generate product ZnS.
Zn
2++S
2-→ZnS （3）
Description of drawings
Fig. 1 is with CuInSe
2Film is the afm image that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Fig. 2 is with CuInSe
2Film is the section afm image that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Fig. 3 is with CuInSe
2Film is the thickness map that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Fig. 4 is with CuInSe
2Film is pH value and the transmittance curve integral area figure that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Fig. 5 is with CuInSe
2Film is the current density transmittance curve integral area graph of a relation that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Fig. 6 is with CuInSe
2Film is that the matrix galvanic deposit prepares the depositing time of solar cell buffer layer ZnS film and the wavelength transmittance curve integral area graph of a relation of film;
Fig. 7 is with CuInSe
2Film is the matrix galvanic deposit wavelength for preparing solar cell buffer layer ZnS film-transmittance curve figure.
Embodiment
The invention will be further described below in conjunction with the embodiment of the best, 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 the matrix galvanic deposit prepares solar cell buffer layer ZnS film is carried out according to following steps:
One, the pre-treatment of conductive glass
Conductive glass is carried out pre-treatment, stand-by;
Two, galvanic deposit prepares CuInSe
2Film
Adopt graphite as anode, as working electrode, anode and working electrode are put into CuInSe with the conductive glass after the step 1 pre-treatment
2Carry out the constant voltage galvanic deposit in the electrodeposit liquid, after the deposition, take out working electrode, clean 5 ~ 10 times with distilled water, and after drying up, namely get CuInSe
2Film;
Three, CuInSe
2The thermal treatment of film
The CuInSe that step 2 is obtained
2Film is 300 ~ 400 ℃, N in temperature
2Under the condition of gas protection, heat-treat 30 ~ 40min;
Four, galvanic deposit prepares the ZnS film
Adopt graphite as anode, with the CuInSe after the step 3 thermal treatment
2Film is as working electrode, anode and working electrode put into the ZnS electrodeposit liquid carry out the constant voltage galvanic deposit, after the deposition, takes out working electrode with distilled water flushing 3 ~ 5 times, and after drying up, namely gets the ZnS film;
Five, the thermal treatment of ZnS film
The ZnS film that step 4 is obtained is 50 ~ 70 ℃, N in temperature
2Under the condition of gas protection, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely finish with CuInSe
2Film is that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Wherein, the CuInSe described in the step 2
2Electrodeposit liquid is the CuSO by 1 ~ 1.5mmol/L
45H
2The In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2Form CuInSe with the Trisodium Citrate of 0.1 ~ 0.3mol/L
2The pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in the step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in the step 4 is the ZnSO by 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 that the temperature of 3 ~ 4, ZnS electrodeposit liquid is 50 ℃ ~ 60 ℃;
Constant voltage electrodeposition condition described in the 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 the film, processing condition comprise its electrolyte ph, current density and depositing time to the impact of film performance to the impact of preparation ZnS film in the high spot reviews galvanic deposit, present embodiment is with CuInSe
2Film is that the transmitance that the matrix galvanic deposit prepares solar cell buffer layer ZnS film has reached 80% ~ 90%, for obtain high-level efficiency, the flexible substrate film solar cell is opened up new way cheaply.
Present embodiment uses electro-deposition method not only greatly to save production cost at copper, indium and selenium film preparation solar cell buffer layer ZnS film, but also has the features such as sedimentation rate is fast, simple to operate, safe, is fit to very much prepare on a large scale the ZnS film.
The ZnS film is nontoxic and have higher energy gap value (about 3.7eV) and not only make between absorption layer and the Window layer in conjunction with tightr, plays simultaneously the structure shock absorption, reduces the effect of lattice mismatch.In addition in the past at CuInSe
2The methods such as the large multiplex magnetron sputtering of preparation ZnS buffer layer, vacuum-evaporation prepare on the film, are difficult to accomplish scale operation owing to sputtering method, method of evaporation have expensive cost simultaneously, and present embodiment selects electro-deposition method at CuInSe
2Prepare its thickness of ZnS film on the film as thin as a wafer, structure is very fine and close, greatly reduces simultaneously production cost, can accomplish scale operation.
The scope of the electrolyte ph that existing galvanic deposit ZnS film uses mostly is=7 or 7 system, be neutrality or alkaline system, the ZnS film transmitance lower (50% ~ 60%) of preparing.The present invention is the galvanic deposit of carrying out in acid (pH＜7) system, is conducive to the generation of S in this individual system, and is converted into S under the effect of electrolysis
2+, thereby 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 has reached 80% ~ 90%, has played excellent translucent effect.
And existing electro-deposition method prepares the ZnS film and is not applied to the solar cell buffer layer, both do not adopted electro-deposition method at CuInSe
2Deposition ZnS film on the film, and adopt galvanic deposit to prepare the ZnS film at acid system and also seldom study, present embodiment has obtained at CuInSe through experimental study
2The optimum process condition of deposition ZnS film on the film.
Present embodiment adopts the cathodic reduction sedimentation mechanism at CuInSe
2Deposition ZnS film is specific as follows: S on the film
2O
3 2-At first at H
+Effect under decomposite S simple substance (so during the deposition of present embodiment the scope of the pH value of electrolytic solution control＜7), then, the S simple substance that decomposites is diffused on the negative electrode under the effect of concentration gradient, obtaining electronics is reduced, because this reactions steps is slower, become the control step of whole electrochemical reaction speed.
S
2O
3 2-+6H
++4e→2S+3H
2O （1）
S+e→S
2- （2）
Be positioned at last near the Zn of substrate
2+With the S that is reduced
2-Combination reaction occurs generate product ZnS.
Zn
2++S
2-→ZnS （3）
Embodiment two: what present embodiment and embodiment one were different is: the conductive glass described in the step 1 is the FTO conductive glass.Other is identical with embodiment one.
Embodiment three: what present embodiment was different from embodiment one or two is: the pre-treatment step described in the step 1 is: clean 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, dehydrated alcohol cleaning conductive glass 1 ~ 2 time and distilled water with washing powder successively and clean conductive glass 5 ~ 10 times, then dry up.Other is identical with embodiment one or two.
Embodiment four: what present embodiment was different from one of embodiment one to three is: the CuInSe described in the step 2
2The pH value of the ZnS electrodeposit liquid described in electrodeposit liquid and the step 4 all is to be 80% H with the quality percentage composition
2SO
4Solution regulate.Other is identical with one of embodiment one to three.
Embodiment five: what present embodiment was different from one of embodiment one to four is: the CuInSe described in the step 2
2The pH value of electrodeposit liquid is 2.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different from one of embodiment one to five is: the constant voltage electrodeposition condition described in the step 2 is: voltage is 1.2V, and depositing time is 60min.Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different from one of embodiment one to six is: the pH value of the ZnS electrodeposit liquid described in the step 4 is 3.5.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different from one of embodiment one to seven is: the temperature of the ZnS electrodeposit liquid described in the step 4 is 60 ℃.Other is identical with one of embodiment one to seven.
Embodiment nine: what present embodiment was different from one of embodiment one to eight is: the constant voltage electrodeposition condition described in the 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: what present embodiment was different from one of embodiment one to nine is: the temperature described in the step 5 is 300 ℃.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 the matrix galvanic deposit prepares solar cell buffer layer ZnS film is carried out according to following steps:
One, the pre-treatment of conductive glass
Select the FTO conductive glass as the body material of galvanic deposit ZnS film, the FTO conductive glass is carried out pre-treatment, wherein, pre-treatment step is: clean the FTO conductive glass 1 time → distill 8 times → acetone of washing FTO conductive glass with washing powder and clean the FTO conductive glass 1 time → distill 1 time → distillation of 8 times → dehydrated alcohol of washing FTO conductive glass cleaning FTO conductive glass washing FTO conductive glass 8 times, dry up the FTO conductive glass stand-by after the pre-treatment;
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 to be mixed with CuInSe
2Electrodeposit liquid is 80% H with the quality percentage composition
2SO
4Regulate CuInSe
2Electrodeposit liquid pH value to 2;
The preparation of b.ZnS electrodeposit liquid
Take by weighing the ZnSO of 0.1mol/L
4, the NaS of 0.2mol/L
2O
3Add respectively a certain amount of distilled water with the Trisodium Citrate of 0.1mol/L medicine is all dissolved, with the pH value to 3.5 of vitriol oil regulator solution, the process of regulating pH is to carry out under the condition of stirring, the solution that configures is kept be ready for galvanic deposit.
Three, galvanic deposit prepares CuInSe
2Film
Galvanic deposit prepares CuInSe
2Film adopts two electrode system constant voltage galvanic deposit, and as anode, the FTO conductive glass after the step 1 pre-treatment is put into electrode the CuInSe of step 2 preparation as negative electrode (working electrode) with graphite
2Carry out electrodeposit reaction in the electrodeposit liquid; Wherein, deposition voltage is 1.2V, and electrodeposition time is 60min, takes out negative electrode (working electrode) after deposition is finished and cleans and dry up with distilled water, namely gets CuInSe
2Film;
Four, CuInSe
2The thermal treatment of film
The CuInSe that step 3 is obtained
2Film is 300 ℃, N in temperature
2Thermal treatment under the condition of protection, heat treatment time is 30min;
Five, galvanic deposit prepares the ZnS film
Galvanic deposit prepares the ZnS film and adopts two electrode systems to carry out Constant Electric Current deposition, with graphite as anode, the CuInSe after the step 4 thermal treatment
2Film is as negative electrode (working electrode), with the ZnS electrodeposit liquid of step 2 preparation put into thermostat water bath heat reach 60 ℃ after, electrode is put into electrolytic solution carries out electrodeposit reaction, wherein, voltage is 2.5V in the electrodeposition process, and current density is 1.5mA/cm
2, the temperature of electrolytic solution is 60 ℃, and electrodeposition time is 6min, and deposition is taken out negative electrode (working electrode) with the residual electrolytic solution of the clean film surface of distilled water flushing after finishing, and then dries up with blower, namely gets the ZnS film;
Six, the thermal treatment of ZnS film
The ZnS film that the step 5 galvanic deposit is obtained is at 300 ℃ of temperature, N
2Thermal treatment under the condition of protection, heat treatment time is 1h, thermal treatment is namely finished with CuInSe after cooling to room temperature with the furnace afterwards
2Film is that the matrix galvanic deposit prepares solar cell buffer layer ZnS film.
This test is with CuInSe
2Film be the solar cell buffer layer ZnS film for preparing of matrix galvanic deposit three-dimensional AFM figure as shown in Figure 1, film distribution uniform texture is fine and close as seen from Figure 1, is spherical particle and distributes.
Fig. 2 is with CuInSe
2Film is the section afm image of the solar cell buffer layer ZnS film for preparing of matrix galvanic deposit, as can be seen from the figure the ZnS film as thin as a wafer, Fig. 3 is with CuInSe
2Film is the thickness map of the solar cell buffer layer ZnS film for preparing of matrix galvanic deposit, as can be seen from the figure, the thickness of expression ZnS film between two arrows, its mean thickness fluctuates near 83.90nm, can play the effect of structure buffering fully, be suitable as very much the buffer layer of solar cell.
Analyze by the galvanic deposit parameter to this test, investigate different parameters to the impact of ZnS film transmitance, specific as follows:
1) the pH value is on the impact of ZnS film transmitance
By changing the pH value of the ZnS electrodeposit liquid in this testing sequence five, other Parameter Conditions is constant, then carry out ZnS thin-film electro deposition according to the method for this test, investigate the pH value to the impact of ZnS film transmitance, the result as shown in Figure 4, Fig. 4 is that the pH value is respectively 3.0,3.25,3.5,3.75 and the transmittance curve integral area figure of 4.0 o'clock films, as can be seen from the figure originally the transmitance of film increases along with the increase of pH value, the transmittance curve integral area of film reaches maximum when the pH value is 3.5, when pH value transmitance greater than 3.5 time descends on the contrary, because the excess deposition of S simple substance caused the film transmitance to reduce when the pH value was low, contain excessive Zn simple substance when the pH value is higher in the film, thus the present invention to select the pH value of galvanic deposit be 3.5 as optimum pH value.
2) current density is on the impact of ZnS film transmitance
Prepare the current density of ZnS film by changing five galvanic deposit of this testing sequence, other Parameter Conditions is constant, then carries out ZnS thin-film electro deposition according to the method for this test, investigates current density to the impact of ZnS film transmitance, and the result as shown in Figure 5.
Fig. 5 is the wavelength transmittance curve integral area graph of a relation of ZnS film under the different current densities, and having measured respectively current density in the test is 1.5mA/cm
2, 2.0mA/cm
2, 2.5mA/cm
2And 3.0mA/cm
2The time ZnS film transmitance, as can be seen from Figure 5 the through performance of the increase film of current density reduces gradually, wherein current density is 1.5mA/cm
2The film transmitance the highest, reach 80% ~ 90% at UV-visible region, and current density is 3.0mA/cm
2The film transmitance minimum less than 10%, therefore selecting current density is 1.5mA/cm
2The optimum current density that is used as testing, this moment, film was 80% ~ 90% in the transmitance of visible region.
3) depositing time is on the impact of ZnS film transmitance
Prepare the depositing time of ZnS film by changing five galvanic deposit of this testing sequence, other Parameter Conditions is constant, then carries out ZnS thin-film electro deposition according to the method for this test, investigates depositing time to the impact of ZnS film transmitance, and the result as shown in Figure 5.
Fig. 6 is the wavelength transmittance curve integral area graph of a relation of ZnS film under the different depositing times, measured the transmittance curve that depositing time is respectively ZnS film under 6min, 8min and the 10min in the test, as can be seen from Figure 6 the transmitance of film reduces gradually along with the increase of depositing time, wherein the transmitance of film is maximum when depositing time is 6min, has reached more than 83% at visible region.
By above-mentioned test as can be known, the optimum process condition of galvanic deposit ZnS film is: the pH value selects 3.5; Current density is selected 1.5mA/cm
2Depositing time is selected 6min; Depositing temperature is selected 60 ℃; Thermal treatment temp is 300 ℃.
The wavelength transmittance curve collection of illustrative plates of the ZnS film that this test obtains as shown in Figure 7, as shown in Figure 7, the ZnS film increases gradually in the transmitance in ultraviolet-visible district, tends to be steady near 700nm, has reached 80% ~ 90% in the transmitance of visible region.
Claims (10)
1. with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that with CuInSe
2Film is that the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film is carried out according to following steps:
One, the pre-treatment of conductive glass
Conductive glass is carried out pre-treatment, stand-by;
Two, galvanic deposit prepares CuInSe
2Film
Adopt graphite as anode, as working electrode, anode and working electrode are put into CuInSe with the conductive glass after the step 1 pre-treatment
2Carry out the constant voltage galvanic deposit in the electrodeposit liquid, after the deposition, take out working electrode, clean 5 ~ 10 times with distilled water, and after drying up, namely get CuInSe
2Film;
Three, CuInSe
2The thermal treatment of film
The CuInSe that step 2 is obtained
2Film is 300 ~ 400 ℃, N in temperature
2Under the condition of gas protection, heat-treat 30 ~ 40min;
Four, galvanic deposit prepares the ZnS film
Adopt graphite as anode, with the CuInSe after the step 3 thermal treatment
2Film is as working electrode, anode and working electrode put into the ZnS electrodeposit liquid carry out the constant voltage galvanic deposit, after the deposition, takes out working electrode with distilled water flushing 3 ~ 5 times, and after drying up, namely gets the ZnS film;
Five, the thermal treatment of ZnS film
The ZnS film that step 4 is obtained is 50 ~ 70 ℃, N in temperature
2Under the condition of gas protection, heat-treat 0.1 ~ 0.2h, cool to room temperature with the furnace, namely finish with CuInSe
2Film is that the matrix galvanic deposit prepares solar cell buffer layer ZnS film;
Wherein, the CuInSe described in the step 2
2Electrodeposit liquid is the CuSO by 1 ~ 1.5mmol/L
45H
2The In of O, 4.5 ~ 5.0mmol/L
2(SO
4)
3, 4 ~ 4.5mmol/L SeO
2Form CuInSe with the Trisodium Citrate of 0.1 ~ 0.3mol/L
2The pH value of electrodeposit liquid is 2 ~ 3;
Constant voltage electrodeposition condition described in the step 2 is: voltage is 1.2 ~ 1.5V, and depositing time is 50 ~ 70min;
ZnS electrodeposit liquid described in the step 4 is the ZnSO by 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 that the temperature of 3 ~ 4, ZnS electrodeposit liquid is 50 ℃ ~ 60 ℃;
Constant voltage electrodeposition condition described in the step 4 is: voltage is 2 ~ 3V, and current density is 1 ~ 2mA/cm
2, depositing time is 4 ~ 6min.
2. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that the conductive glass described in the step 1 is the FTO conductive glass.
3. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that the pre-treatment step described in the step 1 is: clean 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, dehydrated alcohol cleaning conductive glass 1 ~ 2 time and distilled water with washing powder successively and clean conductive glass 5 ~ 10 times, then dry up.
4. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that the CuInSe described in the step 2
2The pH value of the ZnS electrodeposit liquid described in electrodeposit liquid and the step 4 all is to be 80% H with the quality percentage composition
2SO
4Solution regulate.
5. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that the CuInSe described in the step 2
2The pH value of electrodeposit liquid is 2.
6. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, and it is characterized in that the constant voltage electrodeposition condition described in the step 2 is: voltage is 1.2V, and depositing time is 60min.
7. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, and the pH value that it is characterized in that the ZnS electrodeposit liquid described in the step 4 is 3.5.
8. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, and the temperature that it is characterized in that the ZnS electrodeposit liquid described in the step 4 is 60 ℃.
9. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, and it is characterized in that the constant voltage electrodeposition condition described in the step 4 is: voltage is 2.5V, and current density is 1.5mA/cm
2, depositing time is 6min.
10. according to claim 1 with CuInSe
2Film is the method that the matrix galvanic deposit prepares solar cell buffer layer ZnS film, it is characterized in that the temperature described in the step 5 is 300 ℃.
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| CN111697104A (en) * | 2020-06-24 | 2020-09-22 | 哈尔滨理工大学 | Method for preparing copper indium gallium selenide solar cell in full non-vacuum mode |
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