CN109119494A - Copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode and preparation method thereof - Google Patents
Copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode and preparation method thereof Download PDFInfo
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- 239000011669 selenium Substances 0.000 title claims abstract description 56
- 229910052711 selenium Inorganic materials 0.000 title claims abstract description 55
- WUUZKBJEUBFVMV-UHFFFAOYSA-N copper molybdenum Chemical compound [Cu].[Mo] WUUZKBJEUBFVMV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000004888 barrier function Effects 0.000 claims abstract description 87
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 239000010408 film Substances 0.000 claims abstract description 34
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012535 impurity Substances 0.000 claims abstract description 33
- 239000010949 copper Substances 0.000 claims abstract description 22
- 239000010409 thin film Substances 0.000 claims abstract description 22
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 20
- 239000011733 molybdenum Substances 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 15
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 9
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 6
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 5
- NCMAYWHYXSWFGB-UHFFFAOYSA-N [Si].[N+][O-] Chemical class [Si].[N+][O-] NCMAYWHYXSWFGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004544 sputter deposition Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 230000009970 fire resistant effect Effects 0.000 claims description 4
- 229920000307 polymer substrate Polymers 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000151 deposition Methods 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 description 23
- 235000016768 molybdenum Nutrition 0.000 description 17
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910016525 CuMo Inorganic materials 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000013084 building-integrated photovoltaic technology Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
-
- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
-
- 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
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- Electromagnetism (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention discloses a kind of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, including substrate, barrier against impurities, metal conducting layer and the selenium barrier layer being cascading from the bottom to top；Barrier against impurities are Si oxide, silicon nitride, silicon nitrogen oxides, Ti, Zr, Cr, V, Nb, Ta or Ni；Metal conducting layer is Cu or Cu alloy；Selenium barrier layer is single barrier layer or composite barrier, and single barrier layer is molybdenum, molybdenum oxide or molybdenum nitride, and composite barrier is made of two or more stacking of molybdenum, molybdenum oxide, molybdenum nitride；It is sequentially depositing each structure sheaf on substrate using magnetron sputtering and completes preparation；Barrier against impurities and selenium barrier layer are introduced in the back electrode using copper or copper alloy as metal conducting layer, barrier against impurities can prevent the impurity in substrate from spreading to CIGS thin-film light absorbing layer；Selenium barrier layer can prevent diffusion of the selenium element to metal conducting layer, avoid the reaction between selenium and metal conducting layer, it is ensured that the stability of metal conducting layer.
Description
Technical field
The present invention relates to technical field of thin-film solar, specifically a kind of copper-indium-galliun-selenium film solar cell copper-molybdenum
Alloy back electrode and preparation method thereof.
Background technique
In existing solar battery technology, copper indium gallium selenide (abbreviation CIGS) thin-film solar cells has photoelectric conversion
Rate is high, dim light performance is good, at low cost, both can be made into stiff member as formed a film on glass, and can be in flexibility in hard substrates
On substrate, as being made into flexible unit on stainless steel, aluminium and high temperature polymeric materials, most suitable as Photovoltaic Building Integration
(BIPV) the advantages that using receives people's concern, is a kind of solar battery technology for having very much development potentiality.
The theoretical peak efficiency of CIGS thin-film solar cells be 33%, and now laboratory can accomplish most efficiently
Rate just reaches 21.7%, and there are also very big rooms for promotion.There are many CIGS thin film preparation method of solar battery, at present prevailing technology
Have two kinds: one is elder generations to deposit copper and indium gallium CIG metal preformed layer using the method for magnetron sputtering on back electrode/substrate base,
Then selenizing is carried out using pre-deposition selenium or the heat-treating methods that are rapidly heated in hydrogen selenide environment, forms CIGS absorbed layer；
Another kind is to use magnetron sputtering or the method steamed altogether on high temperature back electrode/substrate base while depositing copper, indium, gallium, selenium four
Kind element absorbs layer film to generate CIGS.Back electrode as copper indium gallium selenide, it is necessary to have the following conditions:
One, with certain chemical reaction inertia, to resist corrosion of the selenium to back electrode in CIGS thin film high temperature selenidation process；
Two, conductivity with higher guarantees that CIGS back electrode obtains best electric conductivity with most thin film layer；
Three, the ability that good ohmic contact is formed with same p-type CIGS thin film reduces few sub (electronics) recombination rate of interface,
Improve CIGS hull cell optoelectronic transformation efficiency；
Four, there is blocking capability, diffuse into CIGS absorbed layer in the impurity high temperature selenidation process to prevent substrate surface；
Five, with high light reflectivity, the sunlight not absorbed is reflected back in CIGS light absorbing layer film, thus maximum
Reduce to degree the loss of light.
In all metal materials, molybdenum can meet above-mentioned condition to the maximum extent, be current most popular copper and indium gallium
Selenium hull cell back electrode material.Since the fusing point of molybdenum is high, it is 2623 DEG C, is difficult to deposit with evaporation technique, magnetron sputtering method
Deposition rate is high, film is uniform, adhesive force is good, is the robust techniques of current deposition Mo film, and the molybdenum film as back electrode is thick
Degree is generally between 300~500nm.But molybdenum, as one of rare metal, have a series of disadvantages: the electric conductivity of molybdenum is relatively
Difference, the cost of raw material is relatively high, and magnetron sputtering rate is also relatively slow.
Copper has the advantages that a series of molybdenums do not have as one of most common metal, and electric conductivity is three times of molybdenum, material
Expect 1/4 of cost less than molybdenum, magnetron sputtering deposition velocity is 2 times of molybdenum.But using copper as back electrode material, there is following lack
Point: one, the chemical reaction stability of copper is poor, is easy to be corroded by Se in CIGS high temperature selenidation process, generates CuSe, loses back electricity
The effect of pole electric conductivity；Two, the diffusion of substrate surface impurity cannot effectively be stopped, these impurity are in CIGS high temperature selenidation process
Diffusion reaches CIGS thin film, influences CIGS thin film performance；Three, Cu is spread to CIGS thin film, so that CIGS thin film atomic ratio is lacked of proper care,
Seriously affect the photoelectric properties of CIGS thin film.
Summary of the invention
The purpose of the present invention is to provide a kind of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode and its preparations
Method, it can be ensured that back electrode metal conducting layer keeps stablizing in CIGS thin-film high temperature selenidation process, while back electrode
Good ohmic is formed with CIGS thin-film to contact.
The technical solution adopted by the present invention to solve the technical problems is:
Copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, including substrate, the impurity being cascading from the bottom to top
Barrier layer, metal conducting layer and selenium barrier layer；
The barrier against impurities are Si oxide, silicon nitride, silicon nitrogen oxides, Ti, Zr, Cr, V, Nb, Ta or Ni；
The metal conducting layer is Cu or Cu alloy；
The selenium barrier layer is single barrier layer or composite barrier, and single barrier layer is molybdenum, molybdenum oxide or molybdenum nitride, composite barrier
It is made of two or more stacking of molybdenum, molybdenum oxide, molybdenum nitride.
Further, the substrate is glass substrate, flexible stainless steel substrate or fire resistant polymer substrate.
Further, the barrier against impurities with a thickness of 20~120nm.
Further, the metal conducting layer with a thickness of 100~300nm.
Further, the selenium barrier layer with a thickness of 50~160nm.
The present invention also provides a kind of preparation methods of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, including with
Lower step:
S1, deposited on substrate using magnetron sputtering by Si oxide, silicon nitride, silicon nitrogen oxides, Ti, Zr, Cr, V, Nb,
The barrier against impurities that Ta or Ni is constituted；
S2, the metal conducting layer being made of Cu or Cu alloy is deposited in barrier against impurities surface magnetic control sputtering；
S3, on metal conducting layer surface magnetic control sputtering SEDIMENTARY SELENIUM barrier layer, obtain CIGS thin-film solar electricity of the invention
Pond copper molybdenum alloy back electrode.
Further, the working gas of the magnetron sputtering is argon gas, and reaction gas is nitrogen and oxygen.
The beneficial effects of the present invention are: using copper or copper alloy as the copper-indium-galliun-selenium film solar cell of metal conducting layer
Barrier against impurities and selenium barrier layer are introduced in back electrode, barrier against impurities can prevent the impurity in substrate to CIGS thin-film
Light absorbing layer diffusion, reaches copper indium gallium selenide crystal structure most preferably, while increasing the binding force between substrate and metal conducting layer；
Selenium barrier layer can prevent diffusion of the selenium element to metal conducting layer during high temperature selenizing or copper indium gallium selenide high temperature are co-deposited,
Avoid the reaction between selenium and metal conducting layer, it is ensured that metal conducting layer is steady in copper indium gallium selenide optical absorption layer generating process
It is qualitative, in addition, selenium barrier layer surface reacts during high temperature selenizing or copper indium gallium selenide high temperature are co-deposited with CIGS thin-film
Selenides is generated, is contacted to form good ohmic with CIGS thin-film.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples:
Fig. 1 is the structural schematic diagram of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode of the present invention；
Fig. 2 is the structural schematic diagram of copper-indium-galliun-selenium film solar cell of the present invention.
Specific embodiment
Embodiment one
As shown in Figure 1, the present invention provide copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, including from the bottom to top according to
The secondary substrate 1 being stacked, barrier against impurities 2, metal conducting layer 3 and selenium barrier layer 4；
Substrate 1 is using glass substrate, flexible stainless steel substrate or fire resistant polymer substrate；
Barrier against impurities 2 be SiN, barrier against impurities 2 with a thickness of 20~80nm；
Metal conducting layer 3 be Cu or Cu alloy, metal conducting layer 3 with a thickness of 100~300nm；
Selenium barrier layer 4 includes that the lower barrier layer 4a being mutually laminated and upper barrier layer 4b, lower barrier layer 4a and upper barrier layer 4b are constituted again
Barrier layer is closed, lower barrier layer 4a is molybdenum, and upper barrier layer 4b is molybdenum nitride；Selenium barrier layer 4 with a thickness of 50~160nm.
As shown in connection with fig. 2, the present invention also provides a kind of systems of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode
Preparation Method, comprising the following steps:
S1, using the strain-point glass of 3mm thickness as substrate 1, to substrate 1 by cleaning solution clean and tap water rinse after,
It is impregnated with deionized water, aqueous isopropanol and each 10~30 minutes ultrasonic, most afterwards through being dried with nitrogen；
Cleaned substrate 1 is put into the magnetron sputtered vacuum chamber for being equipped with Si target, is existed using reactive magnetron sputtering technique
1 surface of substrate deposits SiN film, and SiN film is barrier against impurities 2, and operating air pressure is 3mtorr when sputtering, and sputtering power is close
Degree is 8~15W/cm2, the volume ratio between argon working gas, nitrogen and oxygen is Ar/N2/O2=5/5/1, barrier against impurities 2
With a thickness of 80nm；
S2, the substrate 1 on depositing contaminants barrier layer 2 is placed in the magnetron sputtered vacuum chamber for being equipped with Cu target, is splashed using magnetic control
Technique is penetrated, the metal conducting layer 3 being made of Cu is deposited on 2 surface of barrier against impurities；When sputtering, operating air pressure 3mtorr splashes
Penetrating power density is 3~8W/cm2, metal conducting layer 3 with a thickness of 120nm；
S3, the substrate 1 of depositing metal conductive layer 3 is placed in the magnetron sputtered vacuum chamber for being equipped with Mo target, using DC magnetic
The lower barrier layer 4a that is made of in 3 surface sputtering sedimentation of metal conducting layer Mo of technique of control sputtering, operating air pressure is when sputtering
3mtorr, Sputtering power density are 3~8W/cm2, lower barrier layer 4a with a thickness of 20nm；
Then it again using reactive magnetron sputtering technique in the surface lower barrier layer 4a cvd nitride molybdenum film, nitrogenizes molybdenum film and constitutes
Barrier layer 4b；Operating air pressure is 5mtorr when sputtering, and Sputtering power density is 8~15W/cm2, volume between argon gas and nitrogen
Than for Ar/N2/=5/12, upper barrier layer 4b with a thickness of 45nm；
So far, copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode of the present invention is completed.
Then copper indium gallium selenide optical absorption layer, specific steps are prepared on the back electrode are as follows:
S4, the back electrode for obtaining step S3, by deionized water, acetone and aqueous isopropanol impregnate simultaneously ultrasound each 10~30
Minute, most afterwards through being dried with nitrogen；
S5, it clean back electrode substrate is put into copper, indium, gallium, selenium steams in vacuum cavity altogether, the substrate for being deposited with back electrode is added
Heat is to 570 DEG C；
S6, the evaporation rate by controlling copper, indium, gallium, selenium, are co-deposited copper indium gallium selenide optical absorption layer 5, finally obtain copper indium gallium selenide
Thin-film solar cells.
Embodiment two
As shown in Figure 1, the present invention provides copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, including from the bottom to top successively
Substrate 1, barrier against impurities 2, metal conducting layer 3 and the selenium barrier layer 4 being stacked；
Substrate 1 is using glass substrate, flexible stainless steel substrate or fire resistant polymer substrate；
Barrier against impurities 2 are transition metal Ti, Zr, Cr, V, Nb, Ta or Ni, and the present embodiment uses Ti,
Barrier against impurities 2 with a thickness of 20~120nm；
Metal conducting layer 3 be Cu or Cu alloy, the present embodiment use CuMo alloy, Mo atomic ratio be 20~50% between, as
Preferably, it is 20% CuMo alloy as metal conducting layer 3 that the present embodiment, which uses Mo atomic ratio, with a thickness of 100~500nm.
Selenium barrier layer 4 includes the lower barrier layer 4a and upper barrier layer 4b being mutually laminated, lower barrier layer 4a and upper barrier layer 4b structure
At composite barrier, lower barrier layer 4a is molybdenum nitride, and upper barrier layer 4b is molybdenum；Selenium barrier layer 4 with a thickness of 30~80nm.
As shown in connection with fig. 2, the present invention also provides a kind of systems of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode
Preparation Method, comprising the following steps:
S1, using the strain-point glass of 3mm thickness as substrate 1, to substrate 1 by cleaning solution clean and tap water rinse after,
It is impregnated with deionized water, aqueous isopropanol and each 10~30 minutes ultrasonic, most afterwards through being dried with nitrogen；
Cleaned substrate 1 is put into the magnetron sputtered vacuum chamber for being equipped with Ti target, is existed using DC magnetron sputtering process
The barrier against impurities 2 that 1 surface sputtering sedimentation of substrate is made of Ti, when sputtering, operating air pressure 3mtorr, Sputtering power density is
3~8W/cm2, barrier against impurities 2 with a thickness of 20nm；
S2, the substrate 1 on depositing contaminants barrier layer 2 is placed in the magnetron sputtered vacuum chamber for being equipped with molybdenum copper target, molybdenum copper target
Mo atomic ratio is preferably 20%, and using DC magnetron sputtering process, on 2 surface of barrier against impurities, deposition is made of CuMo alloy
Metal conducting layer 3；When sputtering, operating air pressure 3mtorr, Sputtering power density is 3~8W/cm2, the thickness of metal conducting layer 3
For 160nm；
S3, the substrate 1 of depositing metal conductive layer 3 is placed in the magnetron sputtered vacuum chamber for being equipped with Mo target, it is anti-using magnetic control
The technique that should be sputtered nitrogenizes molybdenum film in 3 surface sputtering sedimentation of metal conducting layer, and nitridation molybdenum film constitutes lower barrier layer 4a, sputtering
When operating air pressure be 5mtorr, Sputtering power density be 8~15W/cm2, the volume ratio between argon gas and nitrogen is Ar/N2=5/
12, lower barrier layer 4a with a thickness of 30nm；
Then the upper barrier layer 4b being made of Mo is deposited on the surface lower barrier layer 4a using DC magnetron sputtering process again；When sputtering
Operating air pressure is 3mtorr, and Sputtering power density is 3~8W/cm2, upper barrier layer 4b with a thickness of 20nm；
So far, copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode of the present invention is completed.
Then copper indium gallium selenide optical absorption layer, specific steps are prepared on the back electrode are as follows:
S4, the back electrode for obtaining step S3, by deionized water, acetone and aqueous isopropanol impregnate simultaneously ultrasound each 10~30
Minute, most afterwards through being dried with nitrogen；
S5, it clean back electrode substrate is put into copper, indium, gallium, selenium steams in vacuum cavity altogether, the substrate for being deposited with back electrode is added
Heat is to 570 DEG C；
S6, the evaporation rate by controlling copper, indium, gallium, selenium, are co-deposited copper indium gallium selenide optical absorption layer 5, finally obtain copper indium gallium selenide
Thin-film solar cells.
The above described is only a preferred embodiment of the present invention, being not intended to limit the present invention in any form；Appoint
What those skilled in the art, without departing from the scope of the technical proposal of the invention, all using the side of the disclosure above
Method and technology contents make many possible changes and modifications to technical solution of the present invention, or are revised as the equivalent reality of equivalent variations
Apply example.Therefore, anything that does not depart from the technical scheme of the invention according to the technical essence of the invention do above embodiments
Any simple modification, equivalent replacement, equivalence changes and modification, all of which are still within the scope of protection of the technical scheme of the invention.
Claims (7)
1. copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, which is characterized in that set including stacking gradually from the bottom to top
Substrate, barrier against impurities, metal conducting layer and the selenium barrier layer set；
The barrier against impurities are Si oxide, silicon nitride, silicon nitrogen oxides, Ti, Zr, Cr, V, Nb, Ta or Ni；
The metal conducting layer is Cu or Cu alloy；
The selenium barrier layer is single barrier layer or composite barrier, and single barrier layer is molybdenum, molybdenum oxide or molybdenum nitride, composite barrier
It is made of two or more stacking of molybdenum, molybdenum oxide, molybdenum nitride.
2. copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode according to claim 1, which is characterized in that described
Substrate is glass substrate, flexible stainless steel substrate or fire resistant polymer substrate.
3. copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode according to claim 1, which is characterized in that described
Barrier against impurities with a thickness of 20~120nm.
4. copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode according to claim 1, which is characterized in that described
Metal conducting layer with a thickness of 100~300nm.
5. copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode according to claim 1, which is characterized in that described
Selenium barrier layer with a thickness of 50~160nm.
6. the preparation method of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode, which comprises the following steps:
S1, deposited on substrate using magnetron sputtering by Si oxide, silicon nitride, silicon nitrogen oxides, Ti, Zr, Cr, V, Nb,
The barrier against impurities that Ta or Ni is constituted；
S2, the metal conducting layer being made of Cu or Cu alloy is deposited in barrier against impurities surface magnetic control sputtering；
S3, on metal conducting layer surface magnetic control sputtering SEDIMENTARY SELENIUM barrier layer, obtain CIGS thin-film described in claim 1 too
Positive energy battery copper molybdenum alloy back electrode.
7. the preparation method of copper-indium-galliun-selenium film solar cell copper molybdenum alloy back electrode according to claim 6, feature
It is, the working gas of the magnetron sputtering is argon gas, and reaction gas is nitrogen and oxygen.
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