CN109817732A - A kind of method and device thereof preparing copper indium gallium selenide film battery - Google Patents
A kind of method and device thereof preparing copper indium gallium selenide film battery Download PDFInfo
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- CN109817732A CN109817732A CN201811557674.6A CN201811557674A CN109817732A CN 109817732 A CN109817732 A CN 109817732A CN 201811557674 A CN201811557674 A CN 201811557674A CN 109817732 A CN109817732 A CN 109817732A
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- 238000000034 method Methods 0.000 title claims abstract description 56
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 95
- 230000008020 evaporation Effects 0.000 claims abstract description 94
- 239000000758 substrate Substances 0.000 claims abstract description 91
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 72
- 239000011669 selenium Substances 0.000 claims abstract description 72
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 71
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052802 copper Inorganic materials 0.000 claims abstract description 44
- 239000010949 copper Substances 0.000 claims abstract description 44
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 44
- 229910052738 indium Inorganic materials 0.000 claims abstract description 39
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 238000000137 annealing Methods 0.000 claims abstract description 19
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims abstract description 11
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005477 sputtering target Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 42
- 238000004544 sputter deposition Methods 0.000 claims description 40
- 238000000151 deposition Methods 0.000 claims description 21
- 230000008021 deposition Effects 0.000 claims description 21
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000007740 vapor deposition Methods 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 claims description 2
- 125000003748 selenium group Chemical group *[Se]* 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 60
- 239000010409 thin film Substances 0.000 abstract description 39
- 238000002360 preparation method Methods 0.000 abstract description 13
- 239000011521 glass Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000005361 soda-lime glass Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 3
- 229910000807 Ga alloy Inorganic materials 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 238000006073 displacement reaction Methods 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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Classifications
-
- 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 belongs to coating technique fields, and in particular to a kind of method and device thereof for preparing copper indium gallium selenide film battery.The preparation method includes with copper, indium, and three kinds of elements of gallium are evaporation source, evaporation coating is carried out on substrate, while magnetron sputtering is carried out on substrate by magnetic controlled sputtering target of selenium target, the substrate after obtaining plated film；Substrate after the plated film is made annealing treatment to get copper indium gallium selenium solar film.The preparation method prepares CIGS thin film in such a way that coevaporation method and magnetron sputtering combine, the utilization rate of selenium element is improved while can making CIGS thin film that there is longitudinal gradient of preferable forbidden bandwidth, it overcomes element proportion in CIGS thin film and the fluctuation problem difficult with the debugging of selenium element concentration easily occurs, and magnetron sputtering helps to improve into film uniformity.
Description
Technical field
The invention belongs to coating technique fields, and in particular to a kind of method for preparing copper indium gallium selenide film battery and its dress
It sets.
Background technique
With the rapid growth of world energy sources demand, the energy that traditional fossil energy is not able to satisfy us increasingly is needed
It asks.Solar energy with its cleaning, it is pollution-free the advantages that as one of most potential new energy, at the same time, solar battery into
Fast-developing gold period is entered.
Solar battery is a kind of electrooptical device directly converted solar energy into electrical energy, copper indium gallium selenide film battery
(CIGS) have many advantages, such as that production process is few, have relative cost is low, performance is stable, radiation resistance is strong, photoelectric conversion efficiency is high,
One of research hotspot as solar battery.
The core material of CIGS is CIGS film layer, and the method currently used for production preparation CIGS thin film mainly has selenium after sputtering
Change method and two kinds of coevaporation method, sputtering and selenization technique technology path are weaker to crystallization crystalline controlling ability, when needing adequately to anneal
Between with high temperature could make up this defect to a certain extent, be hardly formed longitudinal gradient of high quality forbidden bandwidth, it is final to turn
It is relatively low to change efficiency.In contrast, coevaporation method is the evaporation coating for carrying out four kinds of copper, indium, gallium, selenium elements on substrate, pass through
The evaporation source of different elements of arranging can be easier to control membranous layer ingredient longitudinal direction gradient, and under conditions of close to 600 DEG C, film layer
Crystalline particle is big, does not need to carry out the i.e. certifiable crystalline quality of stringent annealing process and gradient, the CIGS thin film matter of generation again
Amount is substantially better than sputtering and selenization technique method with conversion ratio, but coevaporation method will use a large amount of evaporation source, and energy consumption is big, and
Selenium is the maximum evaporation material of usage amount in CIGS technology, and evaporation control is difficult, and easily reacting with other elements makes CIGS thin film
Composition and ratio fluctuate, while there are about 60% selenium sources not to act on target material, wastage in the actual production process
It is huge；Selenium source just needs to shut down charge material after ruing out of, and the production cycle of CIGS is seriously limited.
Summary of the invention
In consideration of it, the technical problem to be solved in the present invention is that overcoming selenium in CIGS thin film preparation process in the prior art
Element utilization rate is low, four kinds of element proportions easily fluctuate, and CIGS thin film cannot have high quality forbidden bandwidth and selenium simultaneously
The defects of cycling of elements rate the two advantages of height, to provide a kind of preparation method of copper indium gallium selenide film battery.
In order to solve the above technical problems, present invention employs following technical solutions:
The present invention provides a kind of methods for preparing indium gallium selenium hull cell, this method comprises:
Using three kinds of copper, indium, gallium elements as evaporation source, plated film is carried out to substrate using coevaporation mode, while with selenium target
Magnetron sputtering is carried out to the substrate for magnetic controlled sputtering target；
Substrate after plated film and sputtering is made annealing treatment, copper indium gallium selenium solar film is obtained.
Optionally, the selenium target is the target of the mixture formation of selenium and copper selenide.
Optionally, described when carrying out plated film to substrate using coevaporation mode using three kinds of copper, indium, gallium elements as evaporation source
The sequence of evaporation source are as follows: according to the moving direction of the substrate, with two kinds of gallium, indium elements preceding, the copper is in
Between, two kinds of gallium, indium posterior sequences of element.
Optionally, the sequence of the evaporation source are as follows: according to the moving direction of the substrate, with the gallium, indium, copper, copper,
Gallium, phosphide element sequence to the substrate carry out plated film.
Optionally, when carrying out magnetron sputtering to the substrate as magnetic controlled sputtering target using selenium target, the ginseng of the magnetron sputtering
Number includes:
The magnetron sputtering power of the selenium target is 5-10kw；
The distance between the selenium target and the substrate are 1-1.5m；
The deposition rate of selenium element is 1-5A/S in the selenium target.
Optionally, when carrying out plated film to substrate using coevaporation mode, the environmental parameter of the vapor deposition includes:
The evaporation source spaced set, and the distance between described evaporation source is 30-50cm；
The distance between the evaporation source and the substrate are 1.2-1.5m.
Optionally, the heating power using the gallium element as evaporation source is 0.8-1kw, the deposition rate of the gallium element
For 1-3A/S；
Heating power using the copper as evaporation source is 2-3kw, and the deposition rate of the copper is 1-4A/S；
Heating power using the phosphide element as evaporation source is 0.8-1kw, and the deposition rate of the phosphide element is 1-3A/
S。
Optionally, the temperature of the substrate is 500-600 DEG C；The movement speed of the substrate is 10-50cm/min.
The substrate can be but be not limited to soda-lime glass, quartz glass, vagcor.
Optionally, the CIGS thin film with a thickness of 2-3 μm.
The present invention also provides a kind of device for preparing copper indium gallium selenide film battery, described device includes,
Coating chamber, for carrying out plated film to substrate using coevaporation mode and magnetron sputtering mode；Connect with the coating chamber
The annealing chamber connect；
Wherein, the coating chamber includes,
Transmitting device is arranged in the coating chamber, for carrying and moving the substrate；
Multiple heating containers, the transmitting device is set in the following, and be fixed on the two sides of the coating chamber bottom, be used for
Evaporation source is placed, and on the substrate by the element vapor deposition after evaporation source evaporation；
Sputtering equipment, be arranged described in two sides heating container between, the sputtering equipment towards the transmitting device one
Side is provided with several spouts, and the sputtering equipment is for accommodating target and leading to the element after sputtering to after the target as sputter
It crosses after several spouts spray and is splashed on the substrate.
Optionally, it is equidistantly positioned between multiple heating containers of the same side.
The substrate is mounted on the transmitting device on chamber top, and heating device is arranged above substrate.
Technical solution of the present invention has the advantages that
1. the method provided by the invention for preparing copper indium gallium selenide film battery, including with copper, indium, three kinds of elements of gallium are evaporation
Source carries out evaporation coating on substrate, while carrying out magnetron sputtering on substrate by magnetic controlled sputtering target of selenium target, obtains plated film
Substrate afterwards；Substrate after the plated film is made annealing treatment to get copper indium gallium selenium solar film.The preparation method uses
Coevaporation method can preferably control the gradient and forbidden bandwidth of CIGS thin film；Magnetron sputtering can make selenium element displacement,
It is deposited on more selenium elements on substrate, reduces the chance that selenium reacts with other elements, improve the benefit of selenium element
With rate, the problem of element proportion easily fluctuates in CIGS thin film is overcome；Magnetron sputtering can by control sputtering power simultaneously
Accurately to control the content and film thickness of selenium element in film layer, thus solve the problems, such as that the debugging of selenium element concentration is difficult, and
Magnetron sputtering helps to improve into film uniformity.In addition, it is thin to prepare CIGS in such a way that coevaporation method and magnetron sputtering combine
Film improves the conversion ratio of selenium element while CIGS thin film can be made to have preferable forbidden bandwidth.
2. the method provided by the invention for preparing copper indium gallium selenide film battery, the selenium target is using magnetron sputtering in substrate
Upper plated film, wherein selenium target is the mixture of selenium and copper selenide, during the preparation process, provides not only the selenium member of CIGS thin film
Element, while can also supplement a certain amount of copper.
3. the method provided by the invention for preparing copper indium gallium selenide film battery, three kinds of copper, indium, gallium metallic elements are used
Coevaporation method deposits on substrate, and different metal element is arranged in different positions, and when plated film has sequencing, therefore film layer
The forbidden bandwidth value of the middle tenor difference for forming different layers, the CIGS thin film of this method preparation can reach 1.68eV.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is a kind of flow diagram of method for preparing copper indium gallium selenide film battery provided in an embodiment of the present invention；
Fig. 2 is the main view of the coating chamber provided in an embodiment of the present invention for preparing copper indium gallium selenide film battery；
Fig. 3 is the top view of the coating chamber provided in an embodiment of the present invention for preparing copper indium gallium selenide film battery；
Fig. 4 is that selenium element eruption principle is shown in the coating chamber provided in an embodiment of the present invention for preparing copper indium gallium selenide film battery
It is intended to；
Fig. 5 is the SEM figure of CIGS thin film, and top half is CIGS thin film prepared by embodiment 1 in Fig. 5, and lower half portion is
CIGS thin film prepared by comparative example 1；
Appended drawing reference is as follows:
1- substrate；2- sputtering equipment；3- spout；4- heats container；5- target；6- transmitting device；7- coating chamber.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Shown in Figure 1, the embodiment of the present invention provides a kind of method for preparing copper indium gallium selenide film battery, comprising:
Step S101: using three kinds of copper, indium, gallium elements as evaporation source, plated film is carried out to substrate using coevaporation mode, simultaneously
Magnetron sputtering is carried out to substrate using selenium target as magnetic controlled sputtering target；
Step S102: the substrate after plated film and sputtering is made annealing treatment, copper indium gallium selenium solar film is obtained.
The gradient and forbidden bandwidth of copper in CIGS thin film, indium, gallium can be preferably controlled in the present invention using coevaporation method；
Magnetron sputtering can make selenium element displacement, be deposited on more selenium elements on substrate, reduce selenium and other elements are sent out
The chance of raw reaction, improves the utilization rate of selenium element, overcomes the problem of element proportion easily fluctuates in CIGS thin film；Together
When magnetron sputtering by controlling sputtering power can accurately control the content and film thickness of selenium element in film layer, to solve
The difficult problem of selenium element concentration debugging, and magnetron sputtering helps to improve into film uniformity.In addition, with coevaporation method and magnetic control
It sputters the mode combined and prepares CIGS thin film, CIGS thin film can be made to improve selenium element while there is preferable forbidden bandwidth
Conversion ratio.
In order to further help explain the method for preparing copper indium gallium selenide film battery in the present invention, a kind of energy is first simply introduced
Realize the device that coevaporation and sputtering method combine.
Shown in referring to figs. 2 and 3, the embodiment of the present invention provides a kind of device for preparing copper indium gallium selenide film battery, comprising:
Coating chamber 7 and annealing chamber.Coating chamber 7 includes transmitting device 6, sputtering equipment 2, heating container 4, spout 3, target 5；Wherein, it passes
Defeated device 6 is arranged in coating chamber 7, and is located at the top of coating chamber 7, for carrying and moving substrate 1；Container 4 is heated to be arranged
In the lower section of transmitting device 6, and the two sides of 7 bottom of coating chamber are fixed on, i.e., multiple heating containers 4 line up two rows of settings respectively and exist
7 bottom of coating chamber, heating container 4 is for placing evaporation source, and the element after evaporating evaporation source under the action of heating source steams
Plating is on substrate 1；The setting of sputtering equipment 2 is between two sides heating container 4, i.e., sputtering equipment 2 is arranged in 7 bottom of coating chamber
Heart position, so that heating container 4 is separately positioned on the two sides of sputtering equipment 2, sputtering equipment 2 is mainly used for splashing target
It penetrates, sputtering equipment 2 is a closed chamber, and the side of sputtering equipment 2 towards transmitting device 6 is provided with several spouts 3, sputtering
Device 2 is for accommodating target 5 and being splashed to substrate to passing through the element after sputtering after several spouts 3 spray after target as sputter
On 1.
Optionally, positioned at 4 spaced set of heating container of the same side.To guarantee that evaporation source is equidistant arrangement, have
Conducive to the plated film to substrate.
Certainly, it should be noted that the method provided in the embodiment of the present invention can combine device provided in the present invention
It is realized, can also be realized using other devices.Above-mentioned offer is only based on by specific embodiment detailed description below
Device how to prepare solar energy film.
When preparing copper indium gallium selenide film battery, as shown in Figures 2 and 3, substrate 1 is mounted on transmitting device 6, is transmitted
Device 6 is arranged above chamber, and heating source is arranged above substrate 1, and transmitting device 6 starts to be driven with certain speed, in chamber certainly
Left-to-right is arranged successively metallic element evaporation source, and evaporation source is respectively received in heating container 4, and heating container 4 is equidistant respectively
It is arranged in cavity bottom, 2 two sides of sputtering equipment；The bottom of sputtering equipment is arranged in target 5.Substrate 1 is being deposited and is being splashed
Before penetrating, the heating power and deposition rate of evaporation source, and setting magnetron sputtering parameter is respectively set；Pass through the side of coevaporation
Method three kinds of metallic elements of electro-coppering indium gallium on substrate, the sequence by the way that evaporation source is arranged make copper form gradient and are located at CIGS
The middle position of film gradient such as successively steams evaporation source according to gallium evaporation source, indium evaporation source, copper evaporation source, copper evaporation source, gallium
Rise, the sequence of indium evaporation source is placed sequentially in different heating containers 4, above-mentioned evaporation source is evaporated by heating source, to base
Plate carries out plated film.In sputtering equipment 2 be passed through inert gas simultaneously, make gas under the conditions of magnetron sputtering technique to target 5 into
Row bombardment, wherein target 5 is the target that selenium and selenizing copper form, and sprays selenium and copper selenide in target 5 from spout 3,
It is bottom-up, cloud state substance is formed, is assisted with high temperature resistant distributor, it, will under the action of high-vacuum chamber and high negative pressure
The mixed cloud that selenium and copper selenide are formed is sprayed to substrate, is carried out plated film to substrate, is formed copper indium gallium selenide film battery；Then, right
Substrate 1 after plated film is made annealing treatment.
Plated film is carried out to substrate using coevaporation and magnetron sputtering in order to further illustrate the present invention and forms copper indium gallium selenide
The beneficial effect that hull cell obtains.Verifying explanation is carried out by following embodiment and comparative example.Wherein, selenium target with selenium and
Illustrated for the mixture of copper selenide.
Embodiment 1
A kind of method for preparing copper indium gallium selenium solar film is present embodiments provided, specific as follows:
It in CIGS coating chamber, using soda-lime glass as substrate, is mounted on transmitting device, transmitting device is arranged on chamber
Heating source is arranged in side, glass substrate top, and temperature is 600 DEG C, and transmitting device starts to be driven with the speed of 30cm/min, and chamber is certainly
Left-to-right is arranged successively gallium evaporation source, indium evaporation source, copper evaporation source, copper evaporation source, gallium evaporation source, indium evaporation source, evaporation source it
Between spacing be 1.2m at a distance from 30cm, with substrate, evaporation source is separately positioned on cavity bottom, sputtering equipment two sides, and gallium steams
The heating power to rise is 900w, and the heating power of copper evaporation source is 2500w, and the heating power of indium evaporation source is 900w, gallium member
The deposition rate of element is 2A/S；The deposition rate of copper is 3A/S；The deposition rate of phosphide element is 2A/S；The setting of selenium target exists
The deposition rate in cavity bottom middle position, sputtering power 10kw, selenium element is 5A/S, by the method for coevaporation in glass
Three kinds of metallic elements of electro-coppering indium gallium on substrate, the gradient for forming copper are located at the middle position of CIGS thin film gradient, together
When argon gas is passed through in sputtering equipment, bombard argon gas under the conditions of magnetron sputtering technique to target, make selenium and copper selenide
It is sprayed from spout, it is bottom-up, cloud state substance is formed, auxiliary utilizes distributor with high temperature resistant distributor, in high-vacuum chamber
In addition under the action of high negative pressure, the mixed cloud that selenium and copper selenide are formed is sprayed to glass substrate, the spacing between the spout
For 80cm, then glass substrate obtains CIGS thin film after being transmitted to the annealed processing of annealing chamber, and wherein annealing temperature is 500 DEG C,
Time is 60min.
Embodiment 2
A kind of method for preparing copper indium gallium selenium solar film is present embodiments provided, specific as follows:
It in CIGS coating chamber, using quartz glass as substrate, is mounted on transmitting device, transmitting device is arranged on chamber
Heating source is arranged in side, glass substrate top, and temperature is 600 DEG C, and transmitting device starts to be driven with the speed of 50cm/min, and chamber is certainly
Left-to-right be arranged successively gallium evaporation source, indium evaporation source, copper evaporation source, copper evaporation source, gallium evaporation source, indium evaporation source, gallium evaporation source,
Indium evaporation source, the spacing between evaporation source be 1.5m at a distance from 50cm, with substrate, evaporation source be separately positioned on cavity bottom,
Sputtering equipment two sides, the heating power of gallium evaporation source are 1000w, and the heating power of copper evaporation source is 3000w, and indium evaporation source adds
Thermal power is 1000w, and the deposition rate of gallium element is 3A/S；The deposition rate of copper is 4A/S；The deposition rate of phosphide element
For 3A/S；For the setting of selenium target in cavity bottom middle position, the deposition rate of sputtering power 5kw, selenium element are 1A/S, are passed through
Three kinds of metallic elements of copper and indium gallium are electroplated in the method for coevaporation on the glass substrate, and the gradient for forming copper is located at CIGS thin film
The middle position of gradient, while argon gas is passed through in sputtering equipment, carry out argon gas under the conditions of magnetron sputtering technique to target
Bombardment sprays selenium and copper selenide from spout, bottom-up, forms cloud state substance, assists with high temperature resistant distributor, in Gao Zhen
Plenum chamber utilizes other than distributor under the action of high negative pressure, and the mixed cloud that selenium and copper selenide are formed is sprayed to glass substrate, institute
The spacing stated between spout is 50cm, and then glass substrate obtains CIGS thin film after being transmitted to the annealed processing of annealing chamber, wherein
Annealing temperature is 600 DEG C, time 30min.
Embodiment 3
A kind of method for preparing copper indium gallium selenium solar film is present embodiments provided, specific as follows:
It in CIGS coating chamber, using borosilicate glass as substrate, is mounted on transmitting device, transmitting device is arranged in chamber
Heating source is arranged in top, glass substrate top, and temperature is 600 DEG C, and transmitting device starts to be driven with the speed of 15cm/min, chamber
It is arranged successively gallium evaporation source, indium evaporation source, copper evaporation source, copper evaporation source, gallium evaporation source, indium evaporation source, evaporation source from left to right
Between spacing be 1.4m at a distance from 40cm, with substrate, evaporation source is separately positioned on cavity bottom, sputtering equipment two sides, gallium
The heating power of evaporation source is 800w, and the heating power of copper evaporation source is 2000w, and the heating power of indium evaporation source is 800w, gallium
The deposition rate of element is 1A/S；The deposition rate of copper is 2A/S；The deposition rate of phosphide element is 1A/S；The setting of selenium target
In cavity bottom middle position, the deposition rate of sputtering power 8kw, selenium element are 2A/S, by the method for coevaporation in glass
Three kinds of metallic elements of electro-coppering indium gallium on glass substrate, the gradient for forming copper are located at the middle position of CIGS thin film gradient,
It is passed through argon gas in sputtering equipment simultaneously, bombards argon gas under the conditions of magnetron sputtering technique to target, makes selenium and selenizing
Copper is sprayed from spout, bottom-up, forms cloud state substance, and auxiliary utilizes distribution with high temperature resistant distributor, in high-vacuum chamber
Other than device under the action of high negative pressure, the mixed cloud that selenium and copper selenide are formed is sprayed to glass substrate, between the spout between
Away from for 100cm, then glass substrate obtains CIGS thin film after being transmitted to the annealed processing of annealing chamber, and wherein annealing temperature is 550
DEG C, time 40min.
Comparative example 1
This comparative example provides a kind of method that coevaporation prepares copper indium gallium selenium solar film, specific as follows:
It in CIGS coating chamber, using soda-lime glass as substrate, is mounted on transmitting device, the temperature of heating source above glass substrate
Degree is set as 600 DEG C, and chamber is arranged successively selenium evaporation source, gallium evaporation source, indium evaporation source, selenium evaporation source, copper evaporation from left to right
Source, selenium evaporation source, the heating power of copper gallium evaporation source are 900w, and the heating power of copper evaporation source is 2500w, and indium evaporation source adds
Thermal power is 900w, and the heating power of selenium evaporation source is 1000w, deposits four kinds of members on the glass substrate by the method for coevaporation
Then glass substrate is transmitted to the annealed processing of annealing chamber and obtains CIGS thin film by element, wherein annealing temperature is 500 DEG C, the time
For 60min.
Comparative example 2
This comparative example provides the method that selenizing after a kind of magnetron sputtering prepares copper indium gallium selenium solar film, specifically such as
Under:
In CIGS coating chamber, using soda-lime glass as substrate, the temperature of glass substrate is 600 DEG C, in magnetron sputtering chamber
It is passed through argon gas, 10min pre-sputtering is carried out to target used, the impurity particle of target material surface absorption is removed, passes through copper gallium alloy target
One layer of copper gallium alloy layer is sputtered on substrate, then sputters one layer of indium metal layer with indium target again, and it is prefabricated to form copper indium gallium selenide first
Layer；Then by copper target, indium target and gallium target, magnetron sputtering forms the second preformed layer on the first preformed layer, selenizing heat treatment, the
SEDIMENTARY SELENIUM on two preformed layers, anneals later, obtains CIGS thin film, wherein annealing temperature is 500 DEG C, time 60min.
Test example
The CIGS thin film of testing example 1-3 and comparative example 1-2 preparation, concrete outcome are shown in Table 1.In table 1, copper and indium gallium is preset
Selenium element proportion is in the preceding preset ratio carried out to four kinds of element proportions of preparation CIGS thin film test, practical copper indium gallium selenide element
Proportion is the practical proportion situation of four kinds of elements in the CIGS thin film being prepared, and tests to obtain by EDS；Forbidden bandwidth passes through
Spectrometer, measure obtains.
The performance test results for the CIGS thin film that table 1 embodiment 1-3 and comparative example 1-2 is prepared
As seen from Table 1, CIGS thin film, which is prepared, in embodiment 1-3 can deposit more selenium elements, and four kinds of elements are matched
The fluctuation range of ratio is smaller, and the utilization rate of selenium element can be improved using preparation method provided by the invention；And CIGS thin film
Forbidden bandwidth value will be apparently higher than comparative example 1 (coevaporation method preparation CIGS thin film) and (the selenizing preparation after magnetron sputtering of comparative example 2
CIGS thin film).
From FIG. 4, it can be seen that the lattice accounting of CIGS thin film prepared by embodiment 1 is greater than CIGS prepared by comparative example 1
Film, therefore the crystallinity of CIGS thin film that the present invention is prepared is preferable.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of method for preparing copper indium gallium selenide film battery, which is characterized in that this method comprises:
Using three kinds of copper, indium, gallium elements as evaporation source, plated film is carried out to substrate using coevaporation mode, while using selenium target as magnetic
It controls sputtering target and magnetron sputtering is carried out to the substrate；
Substrate after plated film and sputtering is made annealing treatment, copper indium gallium selenium solar film is obtained.
2. the method according to claim 1 for preparing copper indium gallium selenide film battery, which is characterized in that the selenium target is selenium
The target formed with the mixture of copper selenide.
3. the method according to claim 1 or 2 for preparing copper indium gallium selenide film battery, which is characterized in that with copper, indium, gallium
Three kinds of elements are evaporation source, when carrying out plated film to substrate using coevaporation mode, the sequence of the evaporation source are as follows:
According to the moving direction of the substrate, with two kinds of gallium, indium elements preceding, the copper is in centre, the gallium, indium
Two kinds of posterior sequences of element.
4. the method according to claim 3 for preparing copper indium gallium selenide film battery, which is characterized in that the evaporation source it is suitable
Sequence are as follows:
According to the moving direction of the substrate, the substrate is plated with the sequence of the gallium, indium, copper, copper, gallium, phosphide element
Film.
5. the method according to claim 1 for preparing copper indium gallium selenide film battery, which is characterized in that using selenium target as magnetic control
When sputtering target carries out magnetron sputtering to the substrate, the parameter of the magnetron sputtering includes:
The magnetron sputtering power of the selenium target is 5-10kw；
The distance between the selenium target and the substrate are 1-1.5m；
The deposition rate of selenium element is 1-5A/S in the selenium target.
6. the method according to claim 1 for preparing copper indium gallium selenide film battery, which is characterized in that use coevaporation mode
When carrying out plated film to substrate, the environmental parameter of the vapor deposition includes:
The evaporation source spaced set, and the distance between described evaporation source is 30-50cm；
The distance between the evaporation source and the substrate are 1.2-1.5m.
7. the method according to claim 1 for preparing copper indium gallium selenide film battery, which is characterized in that with gallium element work
Heating power for evaporation source is 0.8-1kw, and the deposition rate of the gallium element is 1-3A/S；
Heating power using the copper as evaporation source is 2-3kw, and the deposition rate of the copper is 1-4A/S；
Heating power using the phosphide element as evaporation source is 0.8-1kw, and the deposition rate of the phosphide element is 1-3A/S.
8. the method according to claim 1 for preparing copper indium gallium selenide film battery, which is characterized in that the temperature of the substrate
It is 500-600 DEG C；The movement speed of the substrate is 10-50cm/min.
9. a kind of device for preparing copper indium gallium selenide film battery, which is characterized in that described device includes:
Coating chamber, for carrying out plated film to substrate using coevaporation mode and magnetron sputtering mode；It is connect with the coating chamber
Annealing chamber；
Wherein, the coating chamber includes:
Transmitting device is arranged in the coating chamber, for carrying and moving the substrate；
Multiple heating containers, the transmitting device is set in the following, and be fixed on the two sides of the coating chamber bottom, for placing
Evaporation source, and on the substrate by the element vapor deposition after evaporation source evaporation；
Sputtering equipment is arranged between the heating container described in two sides, and the side of the sputtering equipment towards the transmitting device is set
Several spouts are equipped with, the sputtering equipment is for accommodating target and the element after sputtering being passed through institute to after the target as sputter
It states after several spouts spray and is splashed on the substrate.
10. device according to claim 9, which is characterized in that between multiple heating containers of the same side etc.
Distance setting.
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