CN107354448A - A kind of CBD reactive deposition device and methods of continuous production ZnS films - Google Patents
A kind of CBD reactive deposition device and methods of continuous production ZnS films Download PDFInfo
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- CN107354448A CN107354448A CN201710666901.8A CN201710666901A CN107354448A CN 107354448 A CN107354448 A CN 107354448A CN 201710666901 A CN201710666901 A CN 201710666901A CN 107354448 A CN107354448 A CN 107354448A
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- 238000000151 deposition Methods 0.000 title claims abstract description 88
- 230000008021 deposition Effects 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000010924 continuous production Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 239000010408 film Substances 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000010409 thin film Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 10
- 239000000498 cooling water Substances 0.000 claims abstract description 10
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims abstract description 9
- 238000004804 winding Methods 0.000 claims abstract description 9
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 12
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 150000003751 zinc Chemical class 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009501 film coating Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 241000201246 Cycloloma atriplicifolium Species 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002061 vacuum sublimation Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1233—Organic substrates
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- 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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Abstract
A kind of CBD reactive deposition device and methods of continuous production ZnS films, described device includes the reactive tank for being built-in with reaction decoction, reactive tank is connected successively by low-temperature zone CBD dislodgers and high temperature section CBD dislodgers to be formed, low-temperature zone CBD dislodgers and high temperature section CBD dislodgers are each configured with respective independent loops, recirculated cooling water is each communicated with to control the low-temperature zone batch mixing casing and high temperature section batch mixing casing of reaction fluid temperature, cleaning and drying box are connected to behind high temperature section CBD dislodgers successively and in front and rear each configuration film roll blowing roller and film roll winding roller；Method includes：Prepare the substrate selected by CIGS flexible thin-film solar cell；Prepare reaction solution；Kapton flexible substrate is delivered into CBD reactive tanks top by transmitting device；The respective independent loops of low-temperature zone CBD reactive depositions groove and high temperature section CBD reactive depositions groove；Deposition substrate is covered in above CBD dislodgers, plates aspect haptoreaction liquid.
Description
Technical field
The present invention relates to a kind of CBD reactive depositions dress suitable for industrial automation chemical bath continuous production ZnS films
Put and method, the CBD reactive depositions device and production system of cushion ZnS films especially in the manufacture of novel environment friendly solar cell
Preparation Method, CIGS flexible thin-film battery cushion is prepared suitable for pollution-free immersion method, belongs to second generation solar cell
Manufacture technical field.
Background technology
CIGS (Cu (In, Ga) Se2, abbreviation CIGS thin film solar cell, has low cost, high efficiency, stability
The advantages that good, it is the generally acknowledged most second generation solar cell of development and market potential.Using the photovoltaic of CIGS absorbed layers
Luminous energy efficiently can be converted directly into electric energy by module.The efficiency of research and development world record of small area battery reaches 22.6% at present,
Component efficiency reaches 16.5%, is most promising a kind of low cost generally acknowledged at present, high efficiency photovoltaic technology.
Cushion ZnS prepared by chemical bath method is one of material for substituting cushion CdS, has pollution-free, high efficiency
The advantages that.Experimental study shows at this stage, deposits ZnS with related chemistry formula, film-substrate need to pass through the low temperature depositing ZnS stages
With the high temperature deposition ZnS stages could successful deposition go out uniform and effective ZnS thin film coatings.
The content of the invention
It is an object of the invention to overcome prior art exist existing for deficiency, and it is simple to provide a kind of structure composition, makes
With convenient and reliable, preparation method is simple, and pollution-free, efficient to be applied to industrial automation chemical bath continuous production ZnS thin
The CBD reactive deposition device and methods of film.
The purpose of the present invention is completed by following technical solution, a kind of CBD of described continuous production ZnS films
Reactive deposition device, it includes being built-in with the reactive tank of reaction decoction, and described reactive tank is by low-temperature zone CBD dislodgers and high temperature
Section CBD dislodgers connect compositions successively, and the low-temperature zone CBD dislodgers and high temperature section CBD dislodgers are each configured with each only
Vertical circulation, each communicate with recirculated cooling water to control the low-temperature zone batch mixing casing and high temperature section mixer of reaction fluid temperature
Body, cleaning and drying box are connected to behind the high temperature section CBD dislodgers successively and in front and rear each configuration film roll blowing
Roller and film roll winding roller, forming one includes film transmission mechanism and the CBD reactive deposition devices continuously run.
As preferred：Described low-temperature zone batch mixing casing and high temperature section batch mixing casing are respectively connected to by pump to be prepared and stores
There is the stock bucket of reaction solution, described low-temperature zone batch mixing casing and high temperature section mixer body phase are intercommunicated, and the low-temperature zone is mixed
Reaction solution in hopper body can lead to high temperature section batch mixing casing at regular time and quantity, continue to supply high temperature section reactive deposition.
As preferred：The reaction solution inlet and outlet of described low-temperature zone batch mixing casing are respectively communicated with the low-temperature zone CBD depositions
Groove, and the liquid level of reaction solution in low-temperature zone CBD dislodgers is contacted with the thin film coating face continued through；Described high temperature section is mixed
The reaction solution inlet and outlet of hopper body are also respectively communicated with the high temperature section CBD dislodgers, and make reaction solution in high temperature section CBD dislodgers
Liquid level contacted with the thin film coating face continued through；The upper part of the low-temperature zone CBD dislodgers and high temperature section CBD dislodgers
The deposition tank cover plate formed with IR heating plates is not configured with.
A kind of CBD reactive depositions device using above-mentioned continuous production ZnS films carries out the side of continuous production ZnS films
Method, it the described method comprises the following steps：
（1）Prepare the substrate selected by CIGS flexible thin-film solar cell, i.e., be coated with 0.1 μm ~ 2.0 μ m-thick molybdenum layers successively
(Mo), 0.2 μm of -5.0 μm of CIGS layer（CIGS）Kapton（PI）；
(2) reaction solution is prepared：Ultra-pure water, ammoniacal liquor, zinc salt and chelating agent, thioacetamide are formulated in each by finite concentration
Stock bucket, low-temperature zone is mixed in by air pump by a certain percentage and high temperature section reaction mixer body circulation uses；
After well mixed, the concentration of zinc salt is 1 ~ 1000mM in decoction, and the concentration of chelating agent is 1 ~ 1000mM, thioacetamide
Concentration is 1 ~ 1000Mm, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
（3）Certain thickness molybdenum layer will be coated with successively（Mo）With CIGS layer（CIGS）Kapton（PI）Flexible substrate
CBD reactive tanks top is delivered to 0.3m/min speed by transmitting device；
（4）CBD reaction precipitations, first paragraph are low-temperature zone reactive tank, and length about 1.0 ~ 6.0m, low-temperature zone reactive tank is interior to circulate low temperature
Reaction decoction in section batch mixing casing, low-temperature zone batch mixing casing lead to recirculated cooling water, and control fluid temperature is at 10 ~ 40 DEG C；
Second segment is high temperature section CBD reactive deposition grooves, length about 1.0 ~ 6.0m, cyclic high-temperature section mixer in high temperature section reactive tank
Reaction decoction in body, reactive deposition groove top cover plate are IR heating plates, reaction solution is heated to 50 by infrared heating mode ~
70 DEG C, now reaction solution and film surface contact surface temperature are 70 ~ 90 DEG C, and high temperature section batch mixing casing leads to recirculated cooling water, controls decoction
Temperature is at 50 ~ 70 DEG C；
（5）Low-temperature zone CBD reactive depositions groove and high temperature section CBD reactive depositions groove each independent loops, and low-temperature zone batch mixing casing
High temperature section batch mixing casing is connected, after decoction circulation certain time, high temperature section batch mixing casing discharges a certain amount of decoction, while will be low
The reaction solution that temperature section has circulated certain time leads to high temperature section batch mixing casing, continues to supply high temperature section reactive deposition, realizes reaction medicine
The recycling of liquid, and supplement related decoction to low-temperature zone batch mixing casing simultaneously；
（6）Deposition substrate is covered in above CBD dislodgers, plates aspect haptoreaction liquid, with 0.05 ~ 3.0m/min speed, according to
It is secondary by low-temperature zone reactive deposition groove and high temperature section reactive deposition groove, realize the deposition production of ZnS film layers；When overall reaction deposits
Between about 4 ~ 40min；
（7）Cleaning, dry, winding.
As preferred：Described step（1）In, the concentration of zinc salt is 1 ~ 1000mM in decoction, the concentration of chelating agent for 1 ~
1000mM, the concentration of thioacetamide is 1 ~ 1000mM, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
Described step（3）In, with step（1）Formula deposition ZnS films, need to pass through the low temperature depositing stage, low temperature need to control
10~40℃。
Described step（4）In, with step（1）Formula deposition ZnS films, depositing temperature are advisable at 70 ~ 90 DEG C;Reaction solution
In the case of 50 ~ 70 DEG C, using IR heater plates, the boundary temperature that decoction contacts with film surface can be made to be reached up to 70 ~ 90 DEG C
To high temperature deposition ZnS temperature conditionss.
As preferred：Described step（3）In, low-temperature zone reaction 1.0 ~ 6.0m of slot length, low temperature depositing time control is 2
Between ~ 30min；0.05 ~ 3.0m/min of substrate transporting velocity；
Described step（4）In, high temperature section reaction 1.0 ~ 6.0m of slot length, high temperature section sedimentation time is controlled in 2 ~ 30min；Substrate
0.05 ~ 3.0m/min of transporting velocity.
Using the present invention, solves ZnS thin film low temperature depositions requirement in technique, and realize the successive sedimentation of ZnS films
Production；The present invention has the features such as structure composition is simple, and easy to use and reliable, preparation method is simple, pollution-free, high efficiency.
Brief description of the drawings
Fig. 1 is the structural representation of device of the present invention.
Label in figure is：1st, unreel, 2, winding, 3, CIGS plating layer films, 4, low-temperature zone reactive tank, 5, high temperature section reaction
Groove, 6, cleaning section casing, 7, dryer section casing, 8 low-temperature zone reaction cycle pipelines, 9 high temperature section reaction cycle pipelines, 10, Tank
L connects Tank H pipelines, and 11, low-temperature zone batch mixing casing Tank L, 12, high temperature section batch mixing casing Tank H, 13, low-temperature zone
Reaction cycle pump, 14 high temperature section reaction cycle pumps, 15, infrared hot plate (IR plates), 16, reaction solution.
Embodiment
The present invention will be described in detail below in conjunction with the accompanying drawings and the specific embodiments：Shown in Fig. 1, a kind of continuous production
The CBD reactive deposition devices of ZnS films, it includes being built-in with the reactive tank of reaction decoction 16, and described reactive tank is by low-temperature zone
CBD dislodgers 4 and high temperature section CBD dislodgers 5 connect composition successively, low-temperature zone CBD dislodgers 4 and high temperature section the CBD deposition
Groove 5 be each configured with respective independent loops, each communicate with recirculated cooling water with control reaction fluid temperature low-temperature zone batch mixing
Casing Tank L 11 and high temperature section batch mixing casing Tank H 12, the high temperature section CBD dislodgers 5 are connected to cleaning successively below
Casing 6 and drying box 7, and in front and rear each configuration film roll blowing roller 1 and film roll winding roller 2, the bag of composition one
The CBD reactive deposition devices for including film transmission mechanism and continuously running.
Shown in figure, described low-temperature zone batch mixing casing Tank L 11 and high temperature section batch mixing casing Tank H 12 are each logical
Pump 13,14 is crossed to be connected to preparation and store the stock bucket of reaction solution, described low-temperature zone batch mixing casing Tank L 11 and high temperature
Section batch mixing casing Tank H 12 are interconnected with connecting tube 10, and the reaction solution in the low-temperature zone batch mixing casing Tank L 11
High temperature section batch mixing casing Tank H 12 can be led at regular time and quantity, continue to supply high temperature section reactive deposition.
Low-temperature zone batch mixing casing Tank H 12 of the present invention reaction solution inlet and outlet are respectively communicated with the low-temperature zone
CBD dislodgers 4, and the liquid level of reaction solution in low-temperature zone CBD dislodgers 4 is contacted with the thin film coating face 3 continued through；It is described
High temperature section batch mixing casing Tank H 12 reaction solution inlet and outlet be also respectively communicated with the high temperature section CBD dislodgers 5, and make height
The liquid level of reaction solution contacts with the thin film coating face 3 continued through in temperature section CBD dislodgers 5；The low-temperature zone CBD dislodgers 4
The deposition tank cover plate with the composition of infrared heating IR heating plates 15 is each configured with the top of high temperature section CBD dislodgers 5.
A kind of method suitable for industrial automation chemical bath continuous production ZnS films, methods described include following step
Suddenly：
（1）Prepare the substrate selected by CIGS flexible thin-film solar cell, i.e., be coated with 0.1 μm ~ 2.0 μ m-thick molybdenum layers successively
(Mo), 0.2 μm of -5.0 μm of CIGS layer（CIGS）Kapton（PI）；
(2) reaction solution is prepared：Ultra-pure water, ammoniacal liquor, zinc salt and chelating agent, thioacetamide are formulated in each by finite concentration
Stock bucket, low-temperature zone is mixed in by air pump by a certain percentage and high temperature section reaction mixer body circulation uses；
After well mixed, the concentration of zinc salt is 1 ~ 1000mM in decoction, and the concentration of chelating agent is 1 ~ 1000mM, thioacetamide
Concentration is 1 ~ 1000Mm, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
（3）Certain thickness molybdenum layer will be coated with successively（Mo）With CIGS layer（CIGS）Kapton（PI）Flexible substrate
CBD reactive tanks top is delivered to 0.05 ~ 3.0m/min speed by transmitting device；
（4）CBD reaction precipitations, first paragraph are low-temperature zone reactive tank, and length about 1.0 ~ 6.0m, low-temperature zone reactive tank is interior to circulate low temperature
Reaction decoction in section batch mixing casing, low-temperature zone batch mixing casing lead to recirculated cooling water, and control fluid temperature is at 10 ~ 40 DEG C；
Second segment is high temperature section CBD reactive deposition grooves, length about 1.0 ~ 6.0m, cyclic high-temperature section mixer in high temperature section reactive tank
Reaction decoction in body, reactive deposition groove top cover plate are IR heating plates, reaction solution is heated to 50 by infrared heating mode ~
70 DEG C, now reaction solution and film surface contact surface temperature are 70 ~ 90 DEG C, and high temperature section batch mixing casing leads to recirculated cooling water, controls decoction
Temperature is at 50 ~ 70 DEG C；
（5）Low-temperature zone CBD reactive depositions groove and high temperature section CBD reactive depositions groove each independent loops, and low-temperature zone batch mixing casing
High temperature section batch mixing casing is connected, after decoction circulation certain time, high temperature section batch mixing casing discharges a certain amount of decoction, while will be low
The reaction solution that temperature section has circulated certain time leads to high temperature section batch mixing casing, continues to supply high temperature section reactive deposition, realizes reaction medicine
The recycling of liquid, and supplement related decoction to low-temperature zone batch mixing casing simultaneously；
（6）Deposition substrate is covered in above CBD dislodgers, plates aspect haptoreaction liquid, with 0.05 ~ 3.0m/min speed, according to
It is secondary by low-temperature zone reactive deposition groove and high temperature section reactive deposition groove, realize the deposition production of ZnS film layers；When overall reaction deposits
Between about 4 ~ 40min；
（7）Cleaning, dry, winding.
Step of the present invention（1）In, the concentration of zinc salt is 1 ~ 1000mM in decoction, the concentration of chelating agent for 1 ~
1000mM, the concentration of thioacetamide is 1 ~ 1000mM, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
Described step（3）In, with step（1）Formula deposition ZnS films, need to pass through the low temperature depositing stage, low temperature need to control
10~40℃。
Described step（4）In, with step（1）Formula deposition ZnS films, depositing temperature are advisable at 70 ~ 90 DEG C；Reaction solution
In the case of 50 ~ 70 DEG C, using IR heater plates, the boundary temperature that decoction contacts with film surface can be made to be reached up to 70 ~ 90 DEG C
To high temperature deposition ZnS temperature conditionss.
Step of the present invention（3）In, low-temperature zone reaction 1.0 ~ 6.0m of slot length, low temperature depositing time control 4 ~
Between 30min；0.05 ~ 3.0m/min of substrate transporting velocity；
Described step（4）In, high temperature section reaction 1.0 ~ 6.0m of slot length, high temperature section sedimentation time is controlled in 4 ~ 30min；Substrate
0.05 ~ 3.0m/min of transporting velocity.
Embodiment 1：（1）Prepare ZnS deposition substrates：From the Kapton that thickness is 1 μm ~ 10 μm（PI）As soft
The substrate of property Thinfilm solar cell assembly, uniform 0.5 μm ~ 1 μm is plated using observing and controlling sputtering method and Vacuum sublimation
Mo layers and 0.5 μm of -1 μm of cigs layer；
（2）Prepare the reaction solution of immersion method：By zinc salt, ammoniacal liquor, thioacetamide, nitrilotriacetic acid trisodium, ultra-pure water by certain
Ratio is mixed and made into reaction solution, then adds in each reaction vessel.Wherein Zn2+ concentration is 0.005M, and nitrilotriacetic acid trisodium is dense
It is 0.005M, ammonia concn 1.0M to spend for 0.015M, thioacetamide concentration；
（3）Reactive deposition：Certain thickness Mo and CIGS flexible substrate will be coated with through low-temperature zone CBD reactive depositions groove and high temperature
Section CBD reactive deposition grooves, realize the deposition of ZnS films.After low-temperature zone CBD reaction solutions are when depositing for one section, high temperature can be led to
Section CBD reactive depositions, realize that reaction solution reuses, while related decoction is supplemented to low-temperature zone CBD grooves；
（4）Cleaning, dry, winding.
Embodiment 2：（1）Prepare ZnS deposition substrates：From the Kapton that thickness is 1 μm ~ 10 μm（PI）As soft
The substrate of property Thinfilm solar cell assembly, uniform 0.5 μm ~ 1 μm is plated using observing and controlling sputtering method and Vacuum sublimation
Mo layers and 0.5 μm of -1 μm of cigs layer；
（2）Prepare the reaction solution of immersion method：By zinc salt, ammoniacal liquor, thioacetamide, nitrilotriacetic acid trisodium, ultra-pure water by certain
Ratio is mixed and made into reaction solution, then adds in each reaction vessel.Wherein Zn2+ concentration is 0.0075M, nitrilotriacetic acid trisodium
Concentration is 0.025M, and thioacetamide concentration is 0.0075M, ammonia concn 1.0M；
（3）Reactive deposition：Certain thickness Mo and CIGS flexible substrate will be coated with through low-temperature zone CBD reactive depositions groove and high temperature
Section CBD reactive deposition grooves, realize the deposition of ZnS films.After low-temperature zone CBD reaction solutions are when depositing for one section, high temperature can be led to
Section CBD reactive depositions, realize that reaction solution reuses, while related decoction is supplemented to low-temperature zone CBD grooves；
（4）Cleaning, winding, dry.
Example described above only expresses the several embodiments of the present invention, and its description is more specific and detailed, but not
Therefore the limitation of the scope to patent of the present invention can be interpreted as.
Claims (6)
1. a kind of CBD reactive deposition devices of continuous production ZnS films, it includes being built-in with the reactive tank of reaction decoction, and it is special
Sign is that described reactive tank is connected successively by low-temperature zone CBD dislodgers and high temperature section CBD dislodgers and forms, the low-temperature zone
CBD dislodgers and high temperature section CBD dislodgers be each configured with respective independent loops, to each communicate with recirculated cooling water anti-to control
The low-temperature zone batch mixing casing and high temperature section batch mixing casing of fluid temperature are answered, is connected to successively behind the high temperature section CBD dislodgers
Cleaning and drying box simultaneously wind roller in front and rear each configuration film roll blowing roller and film roll, and forming one includes film
Transmission mechanism and the CBD reactive deposition devices continuously run.
2. the CBD reactive deposition devices of continuous production ZnS films according to claim 1, it is characterised in that described is low
Temperature section batch mixing casing and high temperature section batch mixing casing are respectively connected to by pump to be prepared and stores the stock bucket of reaction solution, and described is low
Temperature section batch mixing casing and high temperature section mixer body phase are intercommunicated, and the reaction solution in the low-temperature zone mixer body can be at regular time and quantity
Towards high temperature section batch mixing casing, continue to supply high temperature section reactive deposition.
3. the CBD reactive deposition devices of continuous production ZnS films according to claim 1 or 2, it is characterised in that described
The reaction solution inlet and outlet of low-temperature zone batch mixing casing are respectively communicated with the low-temperature zone CBD dislodgers, and make in low-temperature zone CBD dislodgers
The liquid level of reaction solution contacts with the thin film coating face continued through；The reaction solution inlet and outlet of described high temperature section batch mixing casing are also divided
The high temperature section CBD dislodgers are not connected, and plate the liquid level of reaction solution in high temperature section CBD dislodgers and the film continued through
Aspect contacts；The top of the low-temperature zone CBD dislodgers and high temperature section CBD dislodgers is each configured with what is formed with IR heating plates
Deposit tank cover plate.
4. a kind of CBD reactive depositions device using the 1 or 2 or 3 continuous production ZnS films of claim carries out continuous production
The method of ZnS films, it is characterised in that the described method comprises the following steps：
（1）Prepare the substrate selected by CIGS flexible thin-film solar cell, i.e., be coated with 0.1 μm ~ 2.0 μ m-thick molybdenum layers successively
(Mo), 0.2 μm of -5.0 μm of CIGS layer（CIGS）Kapton（PI）；
(2) reaction solution is prepared：Ultra-pure water, ammoniacal liquor, zinc salt and chelating agent, thioacetamide are formulated in each by finite concentration
Stock bucket, low-temperature zone is mixed in by air pump by a certain percentage and high temperature section reaction mixer body circulation uses；
After well mixed, the concentration of zinc salt is 1 ~ 1000mM in decoction, and the concentration of chelating agent is 1-1000mM, thioacetamide
Concentration is 1 ~ 1000Mm, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
（3）Certain thickness molybdenum layer will be coated with successively（Mo）With CIGS layer（CIGS）Kapton（PI）Flexible substrate
CBD reactive tanks top is delivered to 0.05 ~ 3.0m/min speed by transmitting device；
（4）CBD reaction precipitations, first paragraph are low-temperature zone reactive tank, and length about 1.0 ~ 6.0m, low-temperature zone reactive tank is interior to circulate low temperature
Reaction decoction in section batch mixing casing, low-temperature zone batch mixing casing lead to recirculated cooling water, and control fluid temperature is at 10 ~ 40 DEG C；
Second segment is high temperature section CBD reactive deposition grooves, length about 1.0 ~ 6.0m, cyclic high-temperature section mixer in high temperature section reactive tank
Reaction decoction in body, reactive deposition groove top cover plate are IR heating plates, reaction solution is heated to 50 by infrared heating mode ~
70 DEG C, now reaction solution and film surface contact surface temperature are 70 ~ 90 DEG C, and high temperature section batch mixing casing leads to recirculated cooling water, controls decoction
Temperature is at 50 ~ 70 DEG C；
（5）Low-temperature zone CBD reactive depositions groove and high temperature section CBD reactive depositions groove each independent loops, and low-temperature zone batch mixing casing
High temperature section batch mixing casing is connected, after decoction circulation certain time, high temperature section batch mixing casing discharges a certain amount of decoction, while will be low
The reaction solution that temperature section has circulated certain time leads to high temperature section batch mixing casing, continues to supply high temperature section reactive deposition, realizes reaction medicine
The recycling of liquid, and supplement related decoction to low-temperature zone batch mixing casing simultaneously；
（6）Deposition substrate is covered in above CBD dislodgers, plates aspect haptoreaction liquid, with 0.05 ~ 3.0m/min speed, according to
It is secondary by low-temperature zone reactive deposition groove and high temperature section reactive deposition groove, realize the deposition production of ZnS film layers；When overall reaction deposits
Between about 4 ~ 40min；
（7）Cleaning, dry, winding.
5. the method for continuous production ZnS films according to claim 4, it is characterised in that：
Described step（1）In, the concentration of zinc salt is 1 ~ 1000mM in decoction, and the concentration of chelating agent is 1 ~ 1000mM, thio second
The concentration of acid amides is 1 ~ 1000mM, and the concentration of ammoniacal liquor is 0.5 ~ 3.0M；
Described step（3）In, with step（1）Formula deposition ZnS films, need to pass through the low temperature depositing stage, low temperature need to control
10~40℃；
Described step（4）In, with step（1）Formula deposition ZnS films, depositing temperature is at 70 ~ 90 DEG C；Reaction solution is 50 ~ 70
In the case of DEG C, using IR heater plates, the boundary temperature that decoction contacts with film surface can be made to be reached a high temperature up to 70 ~ 90 DEG C
Deposit ZnS temperature conditionss.
6. the method for the continuous production ZnS films according to claim 4 or 5, it is characterised in that：
Described step（3）In, low-temperature zone reaction 1.0 ~ 6.0m of slot length, low temperature depositing time control is between 2 ~ 30min；Lining
Bottom 0.05 ~ 3.0m/min of transporting velocity；
Described step（4）In, high temperature section reaction 1.0 ~ 6.0m of slot length, high temperature section sedimentation time is controlled in 2 ~ 30min；Substrate
0.05 ~ 3.0m/min of transporting velocity.
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