CN113161445A - CdTe thin film solar cell activation process - Google Patents

CdTe thin film solar cell activation process Download PDF

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Publication number
CN113161445A
CN113161445A CN202011645747.4A CN202011645747A CN113161445A CN 113161445 A CN113161445 A CN 113161445A CN 202011645747 A CN202011645747 A CN 202011645747A CN 113161445 A CN113161445 A CN 113161445A
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China
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thin film
solar cell
film solar
activation
cdte
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Inventor
彭寿
汪元元
宋杰林
马立云
殷新建
吴一民
陈瑛
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China Triumph International Engineering Co Ltd
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China Triumph International Engineering Co Ltd
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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
    • H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/0221—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work characterised by the means for moving or conveying the objects or other work, e.g. conveyor belts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/04—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation
    • B05B13/0405—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation with reciprocating or oscillating spray heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B14/00—Arrangements for collecting, re-using or eliminating excess spraying material
    • B05B14/40—Arrangements for collecting, re-using or eliminating excess spraying material for use in spray booths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B14/00—Arrangements for collecting, re-using or eliminating excess spraying material
    • B05B14/40—Arrangements for collecting, re-using or eliminating excess spraying material for use in spray booths
    • B05B14/43—Arrangements for collecting, re-using or eliminating excess spraying material for use in spray booths by filtering the air charged with excess material
    • 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
    • H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
    • H01L31/1864—Annealing
    • 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
    • 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
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a CdTe thin film solar cell activation process, which is characterized in that: providing a CdTe thin film solar cell semi-finished product structure, which comprises a transparent substrate, wherein a bottom electrode is arranged on the substrate, and a CdS/CdSe buffer layer and a CdTe light absorption layer are sequentially deposited on the bottom electrode; preparing an activation solution, and spraying the activation solution on the CdTe light absorption layer to a spraying thickness of 5-30 microns; drying the activation solution, and annealing and heat treating to activate the CdTe light absorption layer. The invention adopts non-contact coating, avoids CdTe film surface damage, has uniform coating, simple and convenient maintenance, and nontoxic and environment-friendly activation solution.

Description

CdTe thin film solar cell activation process
Technical Field
The invention belongs to the technical field of photovoltaic cells, and particularly relates to a CdTe thin film solar cell activation process.
Background
CdTe thin film solar cells are one of the most promising thin film solar cells today due to their high efficiency, low cost, and convenience for large area production. The CdTe thin film solar cell glass for mass production of BIPV is generally prepared into key film layers such as CdS, CdSe buffer layers, CdTe light absorption layers and the like by adopting physical vapor processes such as Vapor Transport Deposition (VTD) or Close Space Sublimation (CSS) and the like, and has the advantages of simple process, uniform film thickness, easiness in control and the like.
However, from the material forming point of view, the CdTe film layer obtained by the physical vapor phase process has non-uniform grain growth condition, smaller grain size and more crystal defects due to the relationship between the heating time and the temperature. And lattice mismatch between CdS or CdSe and CdTe causes a large number of interface states to exist, and carrier recombination in an interface region is increased, so that the method becomes one of main reasons for influencing main performance parameters of a actually prepared CdTe solar cell, such as short-circuit current, open-circuit voltage, filling factors and conversion efficiency, to have larger difference compared with a theoretically expected value, and the conversion efficiency of the CdTe thin-film solar cell is reduced. Thus, the objective requirements are that the crystal grain size is uniform, the crystal defects are fewer, and the defect state caused by the mismatching of the CdS/CdSe and CdTe interface is reduced as much as possible so as to prolong the service life of the carriers and reduce the transmission barrier of the carriers. Therefore, in the actual process design, the CdTe film surface of the substrate after physical deposition needs to be coated with an activation solution, and then subjected to high-temperature post-annealing treatment, so that the crystal grain quality is improved, the problem of mismatch between the CdS/CdSe and CdTe interfaces is solved, and the electrical performance of the CdTe thin-film solar cell is improved.
The traditional process generally adopts a sponge roller to roll and coat CdCl2The method has the advantages of complex maintenance, high failure rate, easy damage of CdTe film surface and sponge roller contamination due to contact coating, poor coating uniformity, expensive material consumption and great harm of cadmium ions to the environment and human body, so the development of a novel CdTe solar cell activation process is really necessary.
Disclosure of Invention
In view of the above disadvantages of the prior art, the present invention is directed to a CdTe thin film battery activation process, which is used to solve the problems of complicated and expensive equipment maintenance, poor coating uniformity and high environmental pollution in the prior art.
To achieve the above and other related objects, the present invention provides a CdTe thin film solar cell activation process, comprising the steps of:
1) providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate, wherein a bottom electrode is arranged on the substrate, and a CdS/CdSe buffer layer and a CdTe light absorption layer are sequentially deposited on the bottom electrode;
2) preparing an activation solution, and spraying the activation solution on the CdTe light absorption layer;
3) drying the activation solution, and annealing and heat treating to activate the CdTe light absorption layer.
Optionally, the activating solution is MgCl2The concentration of the aqueous solution is 300-900 g/L.
Optionally, the activating solution is MgCl2An alcohol solution of (a).
Optionally, the activation solution comprises CaCl2One of aqueous solution, KCl aqueous solution and NaCl aqueous solution.
Optionally, the substrate is one of an ultra-white glass substrate, a tempered glass substrate and an organic glass substrate; the bottom electrode is one of an ITO conductive film layer, an FTO conductive film layer and an AZO conductive film layer.
Optionally, the CdS/CdSe buffer layer is 10-150 nm thick, and the CdTe light absorption layer is 2.0-10.0 μm thick; the deposition method of the buffer layer and the light absorption layer comprises vapor transport deposition and near space sublimation deposition.
Optionally, the concentration of the spraying is 200-1200 mg/m2。
Optionally, the drying and annealing heat treatment is carried out in an activation annealing furnace, wherein the activation temperature is 350-450 ℃, and the duration time is 15-45 min.
Optionally, a window layer is arranged between the bottom electrode and the CdS/CdSe buffer layer, the window layer is an MgZnO film layer, and the thickness of the window layer is 40-70 nm.
Optionally, after the activation process is completed, a back electrode is plated in a magnetron sputtering mode, and the CdTe thin film solar cell is obtained.
The invention also provides a CdTe thin film solar cell activation spraying device, which comprises:
the conveying system is used for conveying the CdTe thin film solar cell semi-finished product structure to enter and exit the spraying equipment;
the spraying system adopts a spray head with a low-pressure high-atomization spray valve to perform reciprocating spraying in the vertical conveying direction of the CdTe thin film solar cell semi-finished product structure through a reciprocating module, and the number of the spray heads is 1-6, so that the uniform and stable coating of the activating solution is realized;
the liquid supply system adopts a pressure pump to supply liquid, and when the liquid supply system works, the pressure pump conveys the activated solution from the solution tank to the spraying system through a liquid inlet pipeline to be sprayed out;
the compressed air and air draft system adopts a downward drainage compressed air principle, is positioned at an inlet and an outlet of the spraying equipment and is used for isolating spraying liquid; the air draft system is positioned at the top end of the spraying equipment and used for exhausting atomized spraying liquid in the cavity of the spraying equipment, and a primary effect filtering device, a medium effect filtering device and a high effect filtering device are arranged in the air draft system;
the recovery system collects the surplus spray waste liquid to a waste liquid tank below the spray, and the pump recovers the waste liquid to a waste liquid device;
the control system comprises electric components such as a spraying controller, a control power supply module, power distribution equipment and the like, and has the automatic protection functions of short circuit, electric leakage and overload.
Optionally, the conveying system is propelled by a conveying belt or a conveying roller, and the propelling speed is 2-8 m/min.
Optionally, the conveying roller is of a structure in which rubber rings are sleeved on a central roller, the central shaft is made of polytetrafluoroethylene or polyether-ether-ketone, the rubber rings are made of polypropylene or silicon rubber, and the rubber rings on adjacent conveying rollers are arranged in a staggered manner.
Optionally, 3-5bar of compressed air is introduced into the low-pressure high-atomization spray valve, so that the activation solution is atomized into 0.5-5bar of fan-shaped spray.
Optionally, the fan-shaped spray surface of the low-pressure high-atomization spray valve is inclined by 10-15 degrees with the conveying roller shaft, so that the uniformity of spraying on the surface of the whole product is ensured.
Optionally, the low-pressure high-atomization spray valve can adjust the spray flow and shape and control the coating thickness.
Optionally, the liquid supply system is provided with a temperature control device to ensure that the temperature of the activation solution sprayed from the spray valve is consistent.
Optionally, the primary filter device is used for filtering dust particles with a size of more than 5 μm and is made of polyester fibers; the medium-efficiency filter device is used for filtering 1-5 mu m dust particles and is made of polyester fibers, and the high-efficiency filter device is used for filtering dust particles below 1 mu m and is made of glass fibers.
As described above, the CdTe thin film solar cell activation process of the present invention has the following beneficial effects: non-contact coating is adopted, so that the CdTe film surface damage is avoided, the coating is uniform, the maintenance is simple and convenient, and the activating solution is non-toxic and environment-friendly.
Drawings
FIG. 1 shows a process flow diagram of a CdTe thin film solar cell activation process of the invention.
FIGS. 2 to 4 are schematic structural diagrams showing steps of the CdTe thin film solar cell activation process of the present invention.
FIG. 5 is a schematic view showing the internal design of an activation spraying device for CdTe thin film solar cell of the present invention.
FIG. 6 is a schematic view of the external design of an apparatus for activating and spraying CdTe thin film solar cell of the present invention.
FIG. 7 is a schematic view of the spraying mechanism of the CdTe thin film solar cell activation spraying device of the invention.
Description of the element reference numerals
100 substrate
200 bottom electrode
300 semiconductor heterojunction
301 CdS/CdSe buffer layers
302 CdTe light absorption layer
400 window layer
500 activated droplets
810 conveying roller
820 spraying system
821 servo motor
822 reciprocating straight-moving mechanism
823 shower nozzle
830 pressure pump
840 forced air system
850 recovery groove
860 draft system
S1-S3: and (5) carrying out the following steps.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
As in the detailed description of the embodiments of the present invention, the cross-sectional views illustrating the device structures are not partially enlarged in general scale for convenience of illustration, and the schematic views are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
For convenience in description, spatial relational terms such as "below," "beneath," "below," "under," "over," "upper," and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these terms of spatial relationship are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. Further, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present.
In the context of this application, a structure described as having a first feature "on" a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features are formed in between the first and second features, such that the first and second features may not be in direct contact.
Referring to fig. 1 to 7, it should be noted that the drawings provided in the present embodiment are only schematic illustrations for explaining the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, number and ratio of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
Referring to fig. 1 to 4, embodiments 1 to 8 are CdTe thin film solar cell activation processes, the window layer 400 in the schematic drawings is an optional structure, and in the embodiments, whether the CdTe thin film solar cell semi-finished product structure is provided with the window layer 400 or not can be selected according to needs, without affecting understanding of the activation process.
Example 1
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is an ultra-white glass substrate; the bottom electrode 200 is an FTO conductive film layer. The CdS/CdSe buffer layer 301 is 80nm thick, and the CdTe light absorption layer 302 is 3 μm thick.
650g/L MgCl was prepared2The aqueous solution is used as an activating solution, the activating solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 4 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 4.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 400 ℃, and the duration is 25min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell.
Example 2
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is an ultra-white glass substrate; the bottom electrode 200 is an FTO conductive film layer. The CdS/CdSe buffer layer 301 is 80nm thick, and the CdTe light absorption layer 302 is 3 μm thick.
Preparation of 900g/L MgCl2The aqueous solution is used as an activating solution, the activating solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 4 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 4.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 400 ℃, and the duration is 25min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell.
Example 3
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is an ultra-white glass substrate; the bottom electrode 200 is an FTO conductive film layer. The CdS/CdSe buffer layer 301 is 80nm thick, and the CdTe light absorption layer 302 is 3 μm thick.
Preparing 300g/L MgCl2The aqueous solution is used as an activating solution, the activating solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 4 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 4.
And transferring the sprayed activation solution 500 into an activation annealing furnace for activation at 400 ℃ for 25min, so that the P-type CdTe light absorption layer is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell.
Example 4
This example uses CdCl2The solution was used as comparative activation solution 500.
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is an ultra-white glass substrate; the bottom electrode 200 is an FTO conductive film layer. The CdS/CdSe buffer layer 301 is 80nm thick, and the CdTe light absorption layer 302 is 3 μm thick.
Preparation of 650g/L CdCl2The aqueous solution is used as an activation solution 500, the activation solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 4 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 4.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 400 ℃, and the duration is 25min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell.
Figure BSA0000230650270000071
Using MgCl2Aqueous solution as activating solution with CdCl2Compared with an aqueous solution, the battery has a near minority carrier lifetime and can replace CdCl2The water solution and the process are more environment-friendly, and the waste liquid after spraying is easy to treat.
Example 5
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is one of a tempered glass substrate and an organic glass substrate; the bottom electrode 200 is an ITO conductive film layer. The CdS/CdSe buffer layer 301 is 10nm thick, and the CdTe light absorption layer 302 is 2.0 μm thick.
Preparation 300g/L MgCl2The ethanol solution is used as an activation solution, the activation solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 8 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 6. The spraying thickness is 6-7 μm.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 350 ℃, and the duration is 15min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell. The minority carrier lifetime of the battery is 1.68 ns.
Example 6
Providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is one of a tempered glass substrate and an organic glass substrate; the bottom electrode 200 is an ITO conductive film layer. The CdS/CdSe buffer layer 301 is 150nm thick, and the CdTe light absorption layer 302 is 10 μm thick.
650g/L of NaCl aqueous solution is prepared as an activation solution, the activation solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 4 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 2. The spraying thickness is 12-13 μm.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 400 ℃, and the duration is 45min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell. The minority carrier lifetime of the battery is 0.25 ns.
Example 7
Providing a CdTe thin film battery semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a MgZnO window layer 400 with the thickness of 40nm, a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is one of a tempered glass substrate and an organic glass substrate; the bottom electrode 200 is an ITO conductive film layer. The CdS/CdSe buffer layer 301 is 50nm thick, and the CdTe light absorption layer 302 is 2.0 μm thick.
Preparing 650g/L KCl aqueous solution as an activation solution 500, spraying the activation solution 500 on the CdTe light absorption layer 302, and propelling the CdTe thin film battery by a conveyor belt or a roller at the propelling speed of 6 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 6. The spraying thickness is 12-13 μm.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 400 ℃, and the duration is 45min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell. The minority carrier lifetime of the battery is 0.2 ns.
Example 8
Providing a CdTe thin film battery semi-finished product structure, which comprises a substrate 100, wherein a bottom electrode 200 is arranged on the substrate 100, and a 70nm MgZnO window layer 400, a CdS/CdSe buffer layer 301 and a CdTe light absorption layer 302 are sequentially deposited on the bottom electrode 200; the substrate 100 is one of a tempered glass substrate and an organic glass substrate; the bottom electrode 200 is an ITO conductive film layer. The CdS/CdSe buffer layer 301 is 50nm thick, and the CdTe light absorption layer 302 is 2.0 μm thick.
650g/L CaCl is prepared2The aqueous solution is used as an activation solution 500, the activation solution 500 is sprayed on the CdTe light absorption layer 302, and the CdTe thin film battery is propelled by a conveyor belt or a roller at the propelling speed of 6 m/min; the spraying adopts the spraying system who has low pressure high atomizing spray valve to pass through the reciprocal spraying of motion module, and shower nozzle quantity is 1. The spraying thickness is 15-16 μm.
And transferring the sprayed activation solution 500 into an activation annealing furnace, wherein the activation temperature is 450 ℃, and the duration is 30min, so that the CdTe light absorption layer 302 is activated.
And after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell. The minority carrier lifetime of the battery is 0.82 ns.
Example 9
As shown in FIGS. 5 to 6: for embodiments 1 to 8, the present embodiment provides an apparatus for activating and spraying CdTe thin film solar cell, including:
and the conveying system is used for conveying the CdTe thin film solar cell semi-finished product structure to enter and exit the spraying equipment. The conveying roller 810 is of a structure that a rubber ring is sleeved on a central roller, the central shaft is made of polytetrafluoroethylene or polyether-ether-ketone, the rubber ring is made of polypropylene or silicon rubber, the rubber rings on adjacent conveying rollers are arranged in a staggered mode, and the propelling speed is 2-8 m/min.
The spraying system 820 adopts a spray head 823 with a low-pressure high-atomization spray valve to spray in a reciprocating manner through a reciprocating straight mechanism 822 driven by a servo motor 821 in the vertical conveying direction of the CdTe thin film solar cell semi-finished product structure as shown in FIGS. 5 and 7, wherein the number of the spray heads 823 is 1-6, so that the uniform and stable coating of the activated solution is realized; 3-5bar of compressed air is introduced into the low-pressure high-atomization nozzle 823, so that the activation solution is atomized into 0.5-5bar of fan-shaped spray; the fan-shaped spray surface of the low-pressure high-atomization spray valve and the conveying roller shaft are inclined by 10-15 degrees, so that the uniformity of spraying on the surface of the whole product is ensured; the low-pressure high-atomization spray valve can adjust the spray flow and shape and control the coating thickness.
A pressure pump 830 is adopted to supply liquid, and when the pressure pump 830 works, the activated solution is conveyed from a solution tank to the spraying system through a liquid inlet pipeline to be sprayed out; the liquid supply system is provided with a temperature control device to ensure the temperature of the activating solution sprayed out of the spray valve to be consistent.
The compressed air system 840 adopts a downward drainage compressed air principle, is positioned at an inlet and an outlet of the spraying equipment and is used for isolating spraying liquid;
the air draft system 860 is positioned at the top end of the spraying equipment and is used for pumping the atomized spraying liquid in the cavity of the spraying equipment, and a primary filtering device, a medium-efficiency filtering device and a high-efficiency filtering device are arranged in the air draft system 860; the primary filter device is used for filtering dust particles with the particle size of more than 5 mu m and is made of polyester fiber; the medium-efficiency filter device is used for filtering 1-5 mu m dust particles and is made of polyester fibers, and the high-efficiency filter device is used for filtering dust particles below 1 mu m and is made of glass fibers.
In the recovery system, the excess spray waste liquid is collected in a recovery tank 850 below the spray, and the waste liquid is recovered by a pump into a waste liquid device.
The control system comprises electric components such as a spraying controller, a control power supply module, power distribution equipment and the like, and has the automatic protection functions of short circuit, electric leakage and overload.
In conclusion, the invention adopts non-contact coating, avoids CdTe film surface damage, has uniform coating, simple and convenient maintenance, and nontoxic and environment-friendly activating solution. Therefore, the present invention effectively overcomes the disadvantages of the prior art and has a high industrial value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (18)

1. A CdTe thin film solar cell activation process is characterized by comprising the following steps:
1) providing a CdTe thin film solar cell semi-finished product structure, which comprises a substrate, wherein a bottom electrode is arranged on the substrate, and a CdS/CdSe buffer layer and a CdTe light absorption layer are sequentially deposited on the bottom electrode;
2) preparing an activation solution, and spraying the activation solution on the CdTe light absorption layer;
3) drying the activation solution, and annealing and heat treating to activate the CdTe light absorption layer.
2. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the activating solution is MgCl2The concentration of the aqueous solution is 300-900 g/L.
3. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the activating solution is MgCl2An alcohol solution of (a).
4. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the activating solution comprises CaCl2One of aqueous solution, KCl aqueous solution and NaCl aqueous solution.
5. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the substrate is one of an ultra-white glass substrate, a toughened glass substrate and an organic glass substrate; the bottom electrode is one of an ITO conductive film layer, an FTO conductive film layer and an AZO conductive film layer.
6. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the CdS/CdSe buffer layer is 10-150 nm thick, and the CdTe light absorption layer is 2.0-10.0 mu m thick; the deposition method of the buffer layer and the light absorption layer comprises vapor transport deposition and near space sublimation deposition.
7. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the spraying concentration is 200-1200 mg/m2。
8. The activation process of CdTe thin film solar cell as defined in claim 1, wherein: the drying and annealing heat treatment is carried out in an activation annealing furnace, the activation temperature is 350-450 ℃, and the duration is 15-45 min.
9. The CdTe thin film solar cell activation process according to any one of claims 1 to 8, wherein: and a window layer is arranged between the bottom electrode and the CdS/CdSe buffer layer, the window layer is an MgZnO film layer, and the thickness of the window layer is 40-70 nm.
10. The CdTe thin film solar cell activation process according to any one of claims 1 to 8, wherein: and after the activation process is finished, plating a back electrode in a magnetron sputtering mode to obtain the CdTe thin film solar cell.
11. A CdTe thin film solar cell activation spraying equipment is characterized in that: the CdTe thin film solar cell activation spraying equipment comprises:
the conveying system is used for conveying the CdTe thin film solar cell semi-finished product structure to enter and exit the spraying equipment;
the spraying system adopts a spray head with a low-pressure high-atomization spray valve to perform reciprocating spraying in the vertical conveying direction of the CdTe thin film solar cell semi-finished product structure through a reciprocating module, and the number of the spray heads is 1-6, so that the uniform and stable coating of the activating solution is realized;
the liquid supply system adopts a pressure pump to supply liquid, and when the liquid supply system works, the pressure pump conveys the activated solution from the solution tank to the spraying system through a liquid inlet pipeline to be sprayed out;
the compressed air and air draft system adopts a downward drainage compressed air principle, is positioned at an inlet and an outlet of the spraying equipment and is used for isolating spraying liquid; the air draft system is positioned at the top end of the spraying equipment and used for exhausting atomized spraying liquid in the cavity of the spraying equipment, and a primary effect filtering device, a medium effect filtering device and a high effect filtering device are arranged in the air draft system;
the recovery system collects the surplus spray waste liquid to a waste liquid tank below the spray, and the pump recovers the waste liquid to a waste liquid device;
the control system comprises electric components such as a spraying controller, a control power supply module, power distribution equipment and the like, and has the automatic protection functions of short circuit, electric leakage and overload.
12. The activation spraying equipment for CdTe thin film solar cell as defined in claim 11, wherein: the conveying system adopts a conveying belt or conveying roller for propulsion, and the propulsion speed is 2-8 m/min.
13. The activation spraying equipment for CdTe thin film solar cell as defined in claim 12, wherein: the conveying roller is of a structure that a rubber ring is sleeved on a central roller, the central shaft is made of polytetrafluoroethylene or polyether-ether-ketone, the rubber ring is made of polypropylene or silicon rubber, and the rubber rings on adjacent conveying rollers are arranged in a staggered mode.
14. The activation spraying equipment for CdTe thin film solar cell as defined in claim 11, wherein: 3-5bar of compressed air is connected to the low-pressure high-atomization spray valve, so that the activation solution is atomized into 0.5-5bar of fan-shaped spray.
15. The activation spraying equipment for CdTe thin film solar cell as defined in claim 14, wherein: the fan-shaped spray surface of the low-pressure high-atomization spray valve and the conveying roller shaft are inclined by 10-15 degrees, and the uniformity of spraying on the surface of the whole product is ensured.
16. The activation spraying equipment for CdTe thin film solar cell as defined in claim 14, wherein: the low-pressure high-atomization spray valve can adjust the spray flow and shape and control the coating thickness.
17. The activation spraying equipment for CdTe thin film solar cell as defined in claim 11, wherein: the liquid supply system is provided with a temperature control device to ensure that the temperature of the activating solution sprayed out of the spray valve is consistent.
18. The activation spraying equipment for CdTe thin film solar cell as defined in claim 11, wherein: the primary filter device is used for filtering dust particles with the particle size of more than 5 mu m and is made of polyester fiber; the medium-efficiency filter device is used for filtering 1-5 mu m dust particles and is made of polyester fibers, and the high-efficiency filter device is used for filtering dust particles below 1 mu m and is made of glass fibers.
CN202011645747.4A 2020-12-31 2020-12-31 CdTe thin film solar cell activation process Pending CN113161445A (en)

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