CN108538955B - Pretreatment device and pretreatment method, buffer layer and preparation method and equipment thereof, solar cell and preparation method and system thereof - Google Patents
Pretreatment device and pretreatment method, buffer layer and preparation method and equipment thereof, solar cell and preparation method and system thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type
- H01L31/0749—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN heterojunction type including a AIBIIICVI compound, e.g. CdS/CulnSe2 [CIS] heterojunction solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to the field of solar cells, and particularly provides pretreatment devices, equipment for preparing a buffer layer, a solar cell and a preparation method of the solar cell.
Description
Technical Field
The invention relates to the field of solar cells, in particular to devices for pretreatment when forming a solar cell buffer layer, devices for forming the solar cell buffer layer, methods for pretreatment when forming the solar cell buffer layer, methods for forming the solar cell buffer layer, the buffer layer formed by the methods, methods for preparing solar cells, the solar cells prepared by the methods, and systems for producing the solar cells.
Background
The solar cell is used as devices for directly converting solar energy into electric energy, has the advantages of various installation forms, safety, no pollution, inexhaustibility and inexhaustibility, and is vigorously developed in recent years.
Copper Indium Gallium Selenide (CIGS) thin film solar cells, which are very important solar cells, generally include a substrate, and a bottom electrode (molybdenum layer), an absorption layer, a buffer layer (cadmium sulfide layer), a zinc oxide layer, a zinc aluminum oxide layer, and a front electrode (Ni-Ag layer, Ni-Al layer, etc.) sequentially stacked on the substrate, wherein layers of bottom electrode thin films are plated on a glass substrate and generally collectively referred to as a back electrode+，Ar+Bombarding a molybdenum target under the acceleration of cathode voltage, and depositing bombarded atoms or atom groups on a glass substrate to form a thin film, wherein the deposition temperature is usually normal temperature to 200 ℃. The absorption layer is generally formed by a three-step co-evaporation method, and specifically, is prepared by co-evaporating In-Ga-Se (In, Ga) after raising the temperature of the substrate to about 300 DEG C2Se3And then turning off the In source, the Ga source and the Se source, raising the temperature to about 550 ℃, turning on the Cu source to obtain a copper-rich CIGS layer, and then preparing a small amount of In-Ga-Se layer on the surface of the copper-rich CIGS layer to ensure that the CIGS layer is lean In copper. The cadmium sulfide layer is usually formed by a chemical water bath method, and specifically, a cadmium source (such as cadmium sulfate, cadmium chloride, cadmium acetate and the like) system is used for preparing the cadmium sulfide (CdS) layer by the chemical water bath method, and the deposition temperature is usually 60-90 ℃. The zinc oxide layer and the zinc aluminum oxide layer can be formed by adopting a radio frequency magnetron sputtering method, specifically, argon is introduced and ionized into Ar in a vacuum environment+，Ar+Bombarding a ZnO target material and a ZnO-Al target material respectively under the acceleration of cathode voltage, and depositing the bombarded ZnO atoms or atomic groups and the ZnO-Al atoms or atomic groups to form films, wherein the deposition temperature is usually normal temperature to 200 ℃. The front electrode is generally formed by electron beam evaporation, specifically, by heating an evaporation material Ni-Ag or Ni-Al or the like under vacuum with a high-energy electron beam to evaporateThe material is vaporized and transported toward the substrate where it condenses to form a thin film.
Through research and development of nearly 30 years, the photoelectric conversion efficiency of the CIGS thin-film solar cell is the highest among all known thin-film solar cells and is which is the photovoltaic cell technology with the greatest development prospect, the CIGS thin-film solar cell is used as a buffer layer, a cadmium sulfide thin film and a CIGS absorption layer thin film jointly form a p-n junction, and the CIGS thin-film solar cell plays an important role in improving the performance of the CIGS thin-film solar cell.
For example, CN102544237A discloses a preparation method of buffer layer materials of copper indium gallium selenide thin-film solar cells, which adopts a chemical water bath deposition method and takes zinc sulfate solution as Zn2+Source of thiourea solution as S2-The method comprises the steps of preparing a chemical reaction precursor by taking ammonia water as a buffering agent and nontoxic sodium citrate as a complexing agent, vertically immersing a substrate with a prepared copper-indium-gallium-selenium absorption layer and a cleaned glass substrate into a solution along the wall of a beaker, sealing the opening of the beaker by using an aluminum foil, and then putting the beaker into a water bath for carrying out constant-temperature reaction to prepare a Zn (O, S) semiconductor film serving as a buffer layer material of the copper-indium-gallium-selenium thin-film solar cell.
Disclosure of Invention
The invention aims to solve the problem that the photoelectric conversion efficiency of a solar cell prepared by the existing method is poor, and provides novel devices for pretreatment in forming a solar cell buffer layer, devices for forming the solar cell buffer layer, methods for pretreatment in forming the solar cell buffer layer, methods for forming the solar cell buffer layer and the buffer layer formed by the methods, methods for preparing the solar cell and the solar cell prepared by the methods, and systems for producing the solar cell.
However, after intensive research, the inventor of the present invention finds that a small amount of air is attached to gaps and holes of the absorption layer due to the large surface roughness of the absorption layer, so that the part of the surface attached with the air cannot contact with a deposition reaction solution to cause buffer layer growth loss, and the part of the absorption layer is still exposed in the air after the chemical water bath deposition is finished, so that the performance of the absorption layer is affected, and further the photoelectric conversion efficiency of the solar cell is affected. And the immersion pretreatment can remove the air adsorbed in the gaps and holes of the absorption layer, so that the buffer layer deposition reaction liquid can be in comprehensive contact with the absorption layer, the chemical water bath deposition film-making defects can be effectively reduced, the comprehensive coverage of the absorption layer is realized, the density, the continuity and the flatness of the buffer layer are improved, the absorption layer is completely protected from being isolated from the air, the oxidation is prevented, and the photoelectric conversion efficiency of the solar cell is finally improved. Based on this, the present invention has been completed.
Specifically, , the invention provides devices for pretreatment in forming a solar cell buffer layer, wherein the pretreatment device comprises a water tray, a vacuum cavity and a water storage container;
the water containing tray is used for containing sample wafers to be treated;
the vacuum cavity is used for placing a water tray for containing sample wafers to be processed, is communicated with the vacuumizing device through a vacuum valve and is communicated with the outside through an air release valve ;
the water storage container is used for injecting water into the water containing tray placed in the vacuum cavity, and the water storage container is communicated with the vacuum cavity through a water injection valve .
In a second aspect, the invention also provides kinds of apparatuses for forming a solar cell buffer layer, wherein the apparatuses comprise a chemical water bath deposition device and the device for performing pretreatment described in the aforementioned , and a solar cell back electrode covered with an absorbing layer enters the chemical water bath deposition device for performing chemical water bath deposition after being pretreated by the device for performing pretreatment so as to form a buffer layer on the surface of the absorbing layer.
In a third aspect, the present invention also provides methods for pre-treating in forming a solar cell buffer layer, wherein the method comprises immersing a solar cell back electrode covered with an absorber layer in water in a vacuum environment.
In a fourth aspect, the invention also provides methods for forming a buffer layer of a solar cell, wherein the method comprises the steps of immersing a back electrode of the solar cell covered with an absorbing layer in water under a vacuum environment, and then putting the back electrode into a deposition reaction liquid to form the buffer layer on the surface of the absorbing layer through chemical water bath deposition.
In a fifth aspect, the present invention also provides a solar cell buffer layer formed by the method of the fourth aspect.
In a sixth aspect, the present invention also provides a method for preparing a solar cell, the method comprising forming an absorber layer, a buffer layer, a zinc oxide layer, a zinc aluminum oxide layer and a front electrode on a bottom electrode of a back electrode of the solar cell in this order, wherein the buffer layer is formed according to the method of the fourth aspect of the present invention.
In a seventh aspect, the present invention also provides a solar cell prepared by the method of the above sixth aspect.
In an eighth aspect, the present invention also provides a system for producing solar cells, the system comprising the apparatus for forming a buffer layer of a solar cell according to the second aspect.
The buffer layer prepared by the method provided by the invention can obviously improve the photoelectric conversion efficiency of the corresponding solar cell.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and constitute a part of this specification, and together with the following detailed description , serve to explain the invention without limiting it.
FIG. 1 is a schematic structural diagram of an apparatus for performing pretreatment according to the present invention.
FIG. 2 is a SEM photograph of the surface of the buffer layer (pretreated) obtained in example 1.
Fig. 3 is a scanning electron micrograph of the surface of the buffer layer (not pretreated) obtained in comparative example 1.
Description of the reference numerals
1-water tray, 2-vacuum chamber, 21-vacuum valve , 22-air release valve , 23-chamber lower part, 24-chamber upper cover, 3-water storage container, 31-water injection valve
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
For numerical ranges, between the endpoints of each range and the individual points, and between the individual points may be combined with each other to yield new numerical ranges or ranges, which should be considered as specifically disclosed herein.
As shown in fig. 1, the apparatus for pre-treating when forming the solar cell buffer layer includes a water tray 1, a vacuum chamber 2 and a water storage container 3;
the water containing tray 1 is used for containing sample wafers to be treated;
the vacuum cavity 2 is used for placing a water containing tray 1 containing sample wafers to be processed, and the vacuum cavity 2 is communicated with a vacuum-pumping device through a vacuum valve 21 and is communicated with the outside through an air release valve 22;
the water storage container 3 is used for injecting water into the water containing tray 1 placed in the vacuum cavity 2, and the water storage container 3 is communicated with the vacuum cavity 2 through a water injection valve 31.
According to the present invention, in order to facilitate the sample wafer to be processed and the water tray to be placed in and taken out of the vacuum chamber 2, it is preferable that the vacuum chamber 2 comprises a chamber lower portion 23 and a chamber upper cover 24 which are detachably connected, and in order to further , a sealing rubber gasket may be provided at a connection portion between the chamber lower portion 23 and the chamber upper cover 24.
When the device for pretreating samples provided by the invention is used for pretreating samples, the samples to be treated (the solar cell back electrode covered with the absorbing layer) are placed in the water containing tray 1 (for convenience of forming a buffer layer in the subsequent process, the absorbing layer of the solar cell back electrode faces upwards), then the water containing tray 1 containing the samples is placed at the bottom of the vacuum cavity 2 and sealed, the air release valve 22 is closed, the vacuum valve 21 is opened to vacuumize the vacuum cavity 2, the vacuum valve 21 is closed when the vacuum degree reaches below-0.1 MPa, then the water injection valve 31 is opened to inject the water stored in the water storage container 3 into the water containing tray 1, the water injection valve 31 is closed and the air release valve 22 is opened after the pressure in the vacuum cavity 2 is basically recovered to the normal pressure, then the water containing tray 1 containing the samples is taken out (the samples are kept in the water completely), and thus the pretreatment is completed.
The equipment for forming the solar cell buffer layer comprises a chemical water bath deposition device and the device for preprocessing, wherein the solar cell back electrode covered with the absorption layer enters the chemical water bath deposition device for chemical water bath deposition after being preprocessed by the device for preprocessing so as to form the buffer layer on the surface of the absorption layer.
When the device for forming the solar cell buffer layer provided by the invention is used for forming the buffer layer, the solar cell back electrode covered with the absorption layer is pretreated by adopting the method, then the obtained water containing tray 1 (keeping the solar cell back electrode covered with the absorption layer completely immersed in water all the time) containing the solar cell back electrode covered with the absorption layer is vertically placed into a chemical water bath deposition device, and deposition reaction liquid for forming the buffer layer is injected to form the buffer layer by adopting a conventional chemical water bath method.
The device for forming the solar cell buffer layer is additionally provided with the device for preprocessing on the basis of the existing chemical water bath deposition device, so that the solar cell back electrode covered with the absorption layer is subjected to water seal preprocessing before chemical water bath deposition, and then conventional chemical water bath deposition is carried out in a water seal state. The chemical water bath deposition device can be selected from conventional devices in the field, for example, a water bath kettle and/or a water bath, or a magnetic stirring thermostatic water tank and/or a water storage device which can be heated and has controllable water temperature.
The method for preprocessing when the solar cell buffer layer is formed comprises the step of immersing the solar cell back electrode covered with the absorption layer in water under a vacuum environment.
Preferably, the vacuum environment is such that the vacuum is-0.1 MPa or less, more preferably-0.1 to-0.04 MPa, further steps are preferably-0.1 to-0.06 MPa, most preferably-0.1 to-0.08 MPa.
In the present invention, the pressures are all absolute pressures.
The method for forming the solar cell buffer layer comprises the steps of immersing a solar cell back electrode covered with an absorption layer in water in a vacuum environment, and then putting the solar cell back electrode into deposition reaction liquid to deposit the buffer layer on the surface of the absorption layer through a chemical water bath, wherein the vacuum environment preferably enables the vacuum degree to be lower than-0.1 MPa, more preferably-0.1 MPa to-0.04 MPa, and the step is preferably-0.1 MPa to-0.06 MPa, and most preferably-0.1 MPa to-0.08 MPa.
Preferably, the water is ultrapure water and/or deionized water.
Preferably, the method for forming the buffer layer of the solar cell of the present invention comprises:
placing the solar cell back electrode covered with the absorption layer in the pretreatment device to immerse the solar cell back electrode in water in a vacuum environment;
recovering the device for pretreatment to normal pressure, and taking out the solar cell back electrode covered with the absorption layer from the device for pretreatment;
forming the buffer layer on the solar cell back electrode covered with the absorption layer,
wherein, before the buffer layer is formed, the solar cell back electrode covered with the absorption layer is always immersed in water from the time when the solar cell back electrode is placed in the device for pretreatment.
According to preferred embodiments of the present invention, the deposition reaction liquid contains cadmium salt, ammonium salt, thiourea and water, wherein the concentration of the cadmium salt is 0.001-0.01 mol/L, the concentration of the ammonium salt is 0.001-0.005 mol/L, the concentration of the thiourea is 0.05-0.2 mol/L, and the pH value of the deposition reaction liquid is 9-12.
The kind of the cadmium salt is not particularly limited in the present invention, and for example, at least kinds selected from cadmium sulfate, cadmium acetate, cadmium chloride and cadmium iodide may be used.
The kind of the ammonium salt is not particularly limited in the present invention, and for example, at least kinds selected from ammonium chloride, ammonium sulfate and ammonium acetate may be used.
According to the present invention, the method of adjusting the pH of the precipitation reaction solution to be alkaline is well known to those skilled in the art, and for example, an alkaline substance may be added to the precipitation reaction solution, wherein the alkaline substance may be at least kinds of ammonia, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate.
The chemical water bath deposition conditions are not particularly limited, and the chemical water bath deposition conditions generally include a temperature of 60-80 ℃, preferably 65-70 ℃; the time can be 5-20 min, preferably 8-12 min.
The invention also provides a solar cell buffer layer formed by the method.
The method for preparing the solar cell comprises the step of sequentially forming an absorption layer, a buffer layer, a zinc oxide layer, a zinc aluminum oxide layer and a front electrode on a bottom electrode of a back electrode of the solar cell, wherein the buffer layer is formed according to the method.
The method for preparing the solar cell is mainly improved in that new methods are adopted to form the buffer layer of the solar cell, and the composition and forming mode of other layer structures can be the same as the prior art, for example, the absorption layer can be a copper indium gallium selenide thin film layer, the front electrode is usually a Ni-Ag layer or a Ni-Al layer, the thickness of the absorption layer can be 1000-3000 nm, preferably 1500-2500 nm, the thickness of the buffer layer can be 30-70 nm, preferably 40-60 nm, the thickness of the zinc oxide layer can be 30-100 nm, preferably 1500-2000 nm, and the thickness of the front electrode can be 300-150 nm, preferably 750-2000 nm.
The invention also provides a solar cell prepared by the method.
The system for producing solar cells of the present invention may further comprise other structures conventional in the prior art, and the system for producing solar cells of the present invention is mainly improved by comprising new devices for forming a buffer layer of a solar cell, and the rest structures may be the same as the prior art, and the present invention is not repeated herein.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the thickness of the film layer was measured using a step meter (manufactured by brueck, germany, model number Dektak XT).
Example 1
(1) Ultrasonic cleaning soda-lime glass substrate (5 cm × 5cm × 3mm in size) in 10 wt% hydrochloric acid for 20min, taking out the glass substrate, washing with deionized water to remove residual acid solution, ultrasonic cleaning the glass substrate in absolute ethyl alcohol for 20min, taking out the glass substrate, washing with deionized water to remove residual alcohol solution, ultrasonic cleaning the glass substrate in ultrapure water for 20min, and ultrasonic cleaning the cleaned glass substrate with N2And (5) drying the air gun for later use.
(2) The preparation method comprises the steps of confirming a tin surface and a non-tin surface of a soda-lime glass substrate by using a tin surface instrument, then arranging the soda-lime glass substrate on a coating frame of a back electrode magnetron sputtering coating vacuum chamber, taking metal molybdenum (with the purity of 99.995% and the thickness of 6mm, the same below) as a target material, taking the non-tin surface as a coating surface, carrying out direct current magnetron sputtering on the non-tin surface of the glass substrate to form a molybdenum layer, specifically, vacuumizing to be below 4.0E-4Pa, heating the glass substrate to 120 ℃, stopping heating after 15 minutes, introducing 30sccm argon, controlling the position of a cold pump plate valve, adjusting the air pressure to 0.7Pa, starting to plate an high-pressure layer after glow and pre-sputtering for 10 minutes, plating for 450s, then adjusting the air pressure to about 0.1Pa, plating a low-pressure layer, plating for 3540s, finally adjusting the air pressure to 0.7Pa, plating a second high-pressure layer, plating for 120s, taking out a sample piece after finishing plating, and obtaining a molybdenum solar cell electrode, wherein the thickness of the molybdenum layer is 972 nm.
(3) Forming an absorption layer on the molybdenum layer, specifically: heating the single-side molybdenum solar cell back electrode to 300 ℃, and then carrying out co-evaporation on the molybdenum layer for 25min by adopting a vacuum coating method to prepare (In, Ga)2Se3And closing the In source, the Ga source and the Se source, raising the temperature to the plating temperature of 500 ℃, starting the Cu source, continuing to perform vapor deposition for 30min to obtain a copper-rich CIGS layer, and finally continuing to perform co-vapor deposition of In-Ga-Se for 10min on the surface of the copper-rich CIGS layer to obtain a small amount of In-Ga-Se layer so as to ensure that the CIGS is poor In copper, thereby obtaining the absorbing layer with the thickness of 2000 nm.
(4) Pretreatment and formation of a buffer layer:
as shown in fig. 1, the solar cell back electrode covered with the absorbing layer obtained in step (3) is placed into a water tray, then the water tray containing the sample is placed at the bottom of a vacuum chamber, the upper cover of the chamber is covered, the air release valve is closed, the vacuum valve is opened to start vacuum pumping, the vacuum valve is closed when the vacuum degree reaches-0.1 MPa, the water injection valve is opened to inject the water stored in the water storage container into the water tray, the water injection valve is closed and the air release valve is opened to introduce air after the water completely submerges the sample, the upper cover of the chamber is opened after the pressure in the vacuum chamber is basically recovered to normal pressure, and the water tray 1 containing the sample is taken out (the sample is kept to be completely submerged in the water).
Vertically placing the water-containing tray after water sealing is finished into a water bath, then sequentially adding 0.001mol/L cadmium sulfate aqueous solution, 0.001mol/L ammonium chloride aqueous solution and 0.05mol/L thiourea aqueous solution, adjusting the pH value of the deposition reaction liquid to 10.5 by using ammonia water, then heating and preserving heat in a water bath at 60 ℃ for 20min, then discharging the deposition reaction liquid, taking out a sample wafer, drying the sample wafer by using nitrogen, and detecting to form a buffer layer with the thickness of 80nm on the absorption layer. The surface of the buffer layer was observed with a scanning electron microscope, and the results are shown in FIG. 2. As can be seen from fig. 2, the buffer layer has been completely covered at the crystal boundaries.
(5) And sequentially forming a zinc oxide layer and a zinc aluminum oxide layer on the buffer layer:
and (5) putting the product obtained in the step (4) on a coating frame of a magnetron sputtering coating vacuum chamber, and performing direct-current magnetron sputtering by taking ZnO as a target material and taking the surface of the buffer layer as a coating surface to form a zinc oxide layer. Specifically, background vacuum pumping is carried out until the background vacuum is below 2.0E-4Pa, argon gas is introduced for 40sccm, the air pressure is adjusted to 0.2Pa by controlling the position of a cold pump plate valve, glow starting and pre-sputtering are carried out for 5 minutes, then the zinc oxide layer is plated for 1200s, and the thickness of the finally obtained zinc oxide layer is 50 nm.
And then, taking ZnO and Al as target materials, and taking the surface of the zinc oxide layer as a film coating surface to perform direct-current magnetron sputtering to form a zinc aluminum oxide layer. Specifically, background vacuum pumping is carried out until the background vacuum is below 2.0E-4Pa, argon gas is introduced for 25sccm, the air pressure is adjusted to 0.15Pa by controlling the position of a cold pump plate valve, glow starting and pre-sputtering are carried out for 5 minutes, then the zinc oxide layer is plated for 1800s, and the thickness of the finally obtained zinc oxide aluminum layer is 150 nm.
(6) And forming a front electrode Ni-Ag layer with the thickness of 200nm on the zinc-aluminum oxide layer by adopting an electron beam evaporation method to finally obtain the CIGS thin-film solar cell, which is recorded as TD 1.
Example 2
(1) - (3): same as in example 1.
(4) Pretreatment and formation of a buffer layer:
as shown in fig. 1, the solar cell back electrode covered with the absorbing layer obtained in step (3) is placed into a water tray, then the water tray containing the sample is placed at the bottom of a vacuum chamber, the upper cover of the chamber is covered, the air release valve is closed, the vacuum valve is opened to start vacuum pumping, the vacuum valve is closed when the vacuum degree reaches-0.1 MPa, the water injection valve is opened to inject the water stored in the water storage container into the water tray, the water injection valve is closed and the air release valve is opened to introduce air after the water completely submerges the sample, the upper cover of the chamber is opened after the pressure in the vacuum chamber is basically recovered to normal pressure, and the water tray 1 containing the sample is taken out (the sample is kept to be completely submerged in the water).
Taking out the water containing tray after water sealing is finished, vertically placing the water containing tray into a water bath, then sequentially adding 0.005mol/L cadmium acetate aqueous solution, 0.003mol/L ammonium acetate aqueous solution and 0.1mol/L thiourea aqueous solution, adjusting the pH value of the deposition reaction solution to 10.5 by adopting ammonia water, then heating and preserving the temperature in a water bath at 60 ℃ for 20min, then discharging the deposition reaction solution, taking out the sample wafer, drying the sample wafer by using nitrogen, and detecting to form a buffer layer with the thickness of 50nm on the absorption layer. The surface of the buffer layer was observed with a scanning electron microscope and the results showed that the buffer layer had been completely covered at the crystal boundaries.
(5) - (6): same as in example 1. The final CIGS thin film solar cell was obtained and was designated TD 2.
Example 3
(1) - (3): same as in example 1.
(4) Pretreatment and formation of a buffer layer:
as shown in fig. 1, the solar cell back electrode covered with the absorbing layer obtained in step (3) is placed into a water tray, then the water tray containing the sample is placed at the bottom of a vacuum chamber, the upper cover of the chamber is covered, the air release valve is closed, the vacuum valve is opened to start vacuum pumping, the vacuum valve is closed when the vacuum degree reaches-0.1 MPa, the water injection valve is opened to inject the water stored in the water storage container into the water tray, the water injection valve is closed and the air release valve is opened to introduce air after the water completely submerges the sample, the upper cover of the chamber is opened after the pressure in the vacuum chamber is basically recovered to normal pressure, and the water tray 1 containing the sample is taken out (the sample is kept to be completely submerged in the water).
Taking out the water containing tray after water sealing is finished, vertically putting the water containing tray into a water bath, then sequentially adding 0.01mol/L cadmium chloride aqueous solution, 0.005mol/L ammonium sulfate aqueous solution and 0.2mol/L thiourea aqueous solution, adjusting the pH value of the deposition reaction liquid to 11 by adopting ammonia water, then heating and preserving the temperature in a water bath at 60 ℃ for 20min, then discharging the deposition reaction liquid, taking out the sample wafer, drying the sample wafer by using nitrogen, and detecting to form a buffer layer with the thickness of 60nm on the absorption layer. The surface of the buffer layer was observed with a scanning electron microscope and the results showed that the buffer layer had been completely covered at the crystal boundaries.
(5) - (6): same as in example 1. The final CIGS thin film solar cell was obtained and was designated TD 3.
Comparative example 1
A solar cell was fabricated according to the method of example 1, except that a pre-treatment step was not included in forming the buffer layer, and the specific steps were as follows:
(1) - (3): same as in example 1.
(4) Forming a buffer layer:
vertically placing the solar cell back electrode covered with the absorption layer into a water bath, then sequentially adding 0.001mol/L cadmium sulfate aqueous solution, 0.001mol/L ammonium chloride aqueous solution and 0.05mol/L thiourea aqueous solution, adjusting the pH value of the deposition reaction liquid to 10.5 by using ammonia water, then heating and preserving heat in a water bath at 60 ℃ for 20min, then discharging the deposition reaction liquid, taking out a sample wafer, drying the sample wafer by using nitrogen, and detecting to form a buffer layer with the thickness of 80nm on the absorption layer. The surface of the buffer layer was observed with a scanning electron microscope, and the obtained result is shown in FIG. 3. As can be seen from fig. 3, there are significant fissures at the crystal boundaries, not covered by the buffer layer.
(5) - (6): same as in example 1. Finally, a CIGS thin film solar cell is obtained and is marked as DTD 1.
Test example
The test example is used for illustrating the test of the photoelectric conversion efficiency of the solar cell.
The photoelectric conversion efficiency of CIGS thin film solar cells was measured using a NEWPORT brand I-V test system model 94023a, tested in the laboratory using standard conditions (STC), test conditions: the temperature is 25 ℃, and the light intensity (AM1.5) is 100mW/cm2。
The results are shown in Table 1.
TABLE 1
| Numbering | Solar cell | Photoelectric conversion efficiency (%) |
| Example 1 | TD1 | 15.7 |
| Example 2 | TD2 | 15.2 |
| Example 3 | TD3 | 14.9 |
| Comparative example 1 | DTD2 | 13.2 |
From the above results, it can be seen that the buffer layer formed by the method provided by the invention can significantly improve the photoelectric conversion efficiency of the corresponding solar cell.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (15)
- A device for pretreatment in forming a solar cell buffer layer, wherein the pretreatment device comprises a water tray, a vacuum cavity and a water storage container;the water containing tray is used for containing sample wafers to be treated;the vacuum cavity is used for placing a water tray for containing sample wafers to be processed, is communicated with the vacuumizing device through a vacuum valve and is communicated with the outside through an air release valve ;the water storage container is used for injecting water into the water containing tray placed in the vacuum cavity, and the water storage container is communicated with the vacuum cavity through a water injection valve .
- 2. The apparatus of claim 1, wherein the vacuum chamber comprises a chamber lower portion and a chamber upper cover that are removably connected.
- The apparatus for forming a buffer layer of a solar cell of the type , wherein the apparatus comprises a chemical bath deposition device and the device for pre-treating as claimed in claim 1 or 2, and the back electrode of the solar cell covered with the absorber layer is pre-treated by the device for pre-treating and then directly enters the chemical bath deposition device for chemical bath deposition to form the buffer layer on the surface of the absorber layer.
- 4. The apparatus of claim 3, wherein the chemical bath deposition device is at least of a water bath and a water bath.
- A method of forming a buffer layer for a solar cell of the type described in claim 5 and , the method comprising:placing the solar cell back electrode covered with the absorbing layer in the device for pretreatment of claim 1 or 2 so as to be immersed in water under a vacuum environment;recovering the device for pretreatment to normal pressure, and taking out the solar cell back electrode covered with the absorption layer from the device for pretreatment;then putting the solar cell back electrode into deposition reaction liquid to form a buffer layer on the surface of the absorption layer of the solar cell back electrode covered with the absorption layer through chemical water bath deposition,wherein, before the buffer layer is formed, the solar cell back electrode covered with the absorption layer is always immersed in water from the time when the solar cell back electrode is placed in the device for pretreatment.
- 6. The method of claim 5, wherein the water is ultrapure water and/or deionized water.
- 7. The method of claim 5, wherein the vacuum environment is such that a vacuum degree is-0.1 Mpa or less.
- 8. The method of claim 5, wherein the vacuum environment is such that the vacuum degree is-0.1 to-0.4 MPa.
- 9. The method of any of claims 5-8, wherein the deposition reaction solution contains cadmium salt, ammonium salt, thiourea and water, and the concentration of cadmium salt is 0.001-0.01 mol/L, the concentration of ammonium salt is 0.001-0.005 mol/L, the concentration of thiourea is 0.05-0.2 mol/L, and the pH of the deposition reaction solution is 9-12.
- 10. The method of claim 9, wherein the cadmium salt is selected from at least of cadmium sulfate, cadmium acetate, cadmium chloride, and cadmium iodide.
- 11. The method of claim 9, wherein the ammonium salt is selected from at least of ammonium chloride, ammonium sulfate, and ammonium acetate.
- 12. A solar cell buffer layer formed by the method of any of claims 5-11.
- A method of making a solar cell comprising sequentially forming an absorber layer, a buffer layer, a zinc oxide layer, a zinc aluminum oxide layer and a front electrode on a bottom electrode of a back electrode of a solar cell, wherein the buffer layer is formed according to the method of any of claims 5-11, .
- 14. A solar cell made by the method of claim 13.
- A system for producing solar cells, of the type , characterized in that it comprises a device for forming a solar cell buffer layer according to claim 3 or 4.
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| CN103811584A (en) * | 2012-11-13 | 2014-05-21 | 台积太阳能股份有限公司 | Metal-Based Solution Treatment Of Cigs Absorber Layer In Thin-Film Solar Cells |
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| CN103811584A (en) * | 2012-11-13 | 2014-05-21 | 台积太阳能股份有限公司 | Metal-Based Solution Treatment Of Cigs Absorber Layer In Thin-Film Solar Cells |
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