CN103606598A - Method for selenizing CIGS absorbing layer of thin film solar cell - Google Patents
Method for selenizing CIGS absorbing layer of thin film solar cell Download PDFInfo
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- CN103606598A CN103606598A CN201310620779.2A CN201310620779A CN103606598A CN 103606598 A CN103606598 A CN 103606598A CN 201310620779 A CN201310620779 A CN 201310620779A CN 103606598 A CN103606598 A CN 103606598A
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- selenizing
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- selenium steam
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010409 thin film Substances 0.000 title claims abstract description 8
- 239000011669 selenium Substances 0.000 claims abstract description 63
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 55
- 238000005507 spraying Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- 238000005336 cracking Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 238000010793 Steam injection (oil industry) Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5866—Treatment with sulfur, selenium or tellurium
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to an absorbing layer of a CIGS solar cell, in particular to a method for selenizing a CIGS absorbing layer of a thin film solar cell. The method comprises the steps of preparing selenium steam, conveying an absorbing layer substrate to a preheating area through a conveying belt to be preheated, conveying the preheated substrate to a selenylation area protected by inert gases, guiding the selenium steam into the selenylation area, spraying the selenium steam to the moving substrate, reacting the substrate coated with the selenium in the selenylation area, conveying the substrate through the conveying belt to a cooling area to be cooled after reaction, and outputting the substrate. The method for spraying the selenium steam to the moving substrate is adopted, spraying is even, and evenness of film formation is improved. After splitting decomposition, the selenium steam can be sprayed again, the activity of the selenium steam is improved, and then the film formation quality is improved.
Description
Technical field
The present invention relates to the absorbed layer of CIGS solar cell, is the selenizing method of CIGS absorbed layer specifically.
Background technology
CIGS thin film solar cell because of its have high conversion efficiency, good, low-cost without light-induced degradation, radiation resistance, be applicable to the advantages such as volume to volume technique large-scale production, be considered to have most the thin film solar cell of development potentiality.This battery typical structure consists of substrate, Mo layer metal back electrode, CIGS layer absorbed layer, CdS resilient coating, Window layer high resistant i:ZnO, low-resistance ZnO:Al, MgF2 antireflective coating and Ni-Al gate electrode.Wherein the preparation of CIGS absorbed layer is the core technology of CIGS solar cell.And polynary coevaporation method is to prepare at present in CIGS absorbed layer technique to be used the most extensively and the most successful method.Polynary coevaporation method is prepared CIGS layer, by copper, indium, gallium, four kinds of elements of selenium, with Se vapor form, reacts the multicomponent alloy phase that chemical combination forms Cu (InxGa1-x) Se2 having on the substrate of uniform temperature.In preparation process, selenium heating evaporation method produces selenium steam with supply reaction needed, and the advantage of this mode is simply, easily goes; But along with the consumption of selenium material can cause selenium source steam generation, change, and then have influence on the stability of selenium evaporation capacity, caused the phenomenons such as reduction, film composition lack of homogeneity, the local nonstoichiometry of reactivity and raw material utilization rate compare.It is generally standing by substrate when spraying selenium steam, and this method makes the selenium of injection even not, affects selenizing effect, thereby reduces the quality of film.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of selenizing method that improves selenium steam spraying uniformity, improves the thin-film solar cells CIGS absorbed layer of selenium steam activity.
The present invention solves the problems of the technologies described above adopted technical scheme: the selenizing method of thin-film solar cells CIGS absorbed layer, and it comprises the following steps:
(1) prepare selenium steam;
(2) by conveyer belt by absorbed layer substrate transfer to preheating zone preheating;
(3) through the substrate transfer of preheating to the selenizing district with inert gas shielding, selenium steam is imported to selenizing district simultaneously, on mobile substrate, spray selenium steam;
(4) substrate that is coated with selenium reacts in selenizing district;
(5) after having reacted, by conveyer belt, substrate transfer is carried out to cooling zone cooling, then by its output.
Further, while preparing selenium steam, first selenium source is heated into selenium steam, then selenium steam is carried out to cracking, then the selenium steam of cracking is imported to selenizing district.
Further, preheating zone temperature maintains 630 ℃--and 680 ℃, and make substrate Gai district insulation 15s-20s.
Further, selenizing district is divided into spraying section, conversion zone and air inlet section successively, and substrate is when spraying section is mobile, to its upper injection selenium steam; After injection completes, substrate transfer to conversion zone reacts, and is delivered to cooling section after having reacted again.
Further, before substrate enters spraying area, first to air inlet section, pass into inert gas, inert gas is discharged successively after air inlet section, conversion zone, spraying section.
Further, the temperature in selenizing district maintains 830 ℃--and 880 ℃, substrate is at the standing 2min-4min of conversion zone.
Further, the rate of temperature fall of described cooling zone is 25 ℃/s--35 ℃/s.
The present invention compared with prior art tool has the following advantages:
1, the present invention adopts the mode of spraying selenium steam to mobile substrate, and not only spraying evenly, improves into film uniformity.
2, selenium steam by cracking after, then spray, improved the activity of selenium steam, and then improved quality of forming film.
3, adopt three subregions to process substrate, and selenizing is distinguished into three sections, improved efficiency and the effect of selenylation reaction.
Embodiment
Selenizing method of the present invention comprises the following steps:
(1) prepare selenium steam; When preparing selenium steam, first selenium source is heated into selenium steam, then selenium steam is carried out to cracking, then the selenium steam of cracking is imported to selenizing district; In implementation process, first solid-state selenium is heated to 200 ℃--and 300 ℃, solid-state selenium generates low activity selenium steam, then SA selenium steam is imported to 400 ℃ that the charged body of plasma forms--500 ℃ of glow discharge zones, thereby make it be cracked into highly active selenium steam, more highly active selenium steam importing selenizing district is sprayed substrate.Selenium steam spraying substrate owing to adopting after cracking, makes selenylation reaction more abundant, has improved quality of forming film.
(2) by conveyer belt by absorbed layer substrate transfer to preheating zone preheating; In preheating zone, can adopt infrared lamp, Halogen lamp LED or induction coil to heat substrate, preheating zone temperature maintains 630 ℃--between 680 ℃, for follow-up selenizing provides favourable temperature conditions.
(3) through the substrate transfer of preheating to the selenizing district with inert gas shielding, selenium steam is imported to selenizing district simultaneously, on mobile substrate, spray selenium steam; In implementation process, should guarantee substrate uniform motion, and control the constant flow of injection apparatus, owing to adopting to the mode of spraying quantitative selenium steam on the substrate of uniform motion, therefore, spray and be very evenly conducive to improve absorbed layer selenizing quality; In order to guarantee selenizing quality, selenizing district is divided into spraying section, conversion zone and air inlet section successively, in spraying section, selenium steam injection apparatus is installed, substrate is when spraying section is mobile, to spraying selenium steam on it, the temperature in selenizing district should maintain 830 ℃--880 ℃, can further improve reaction mass; After injection completes, substrate transfer to conversion zone reacts, and is delivered to cooling section after having reacted again.
(4) in spraying section, while substrate moves, spray selenium steam thereon, after spraying, the substrate that is coated with selenium is transferred is with the conversion zone that is delivered to selenizing district to react; In order to improve the quality of reaction, before substrate enters spraying area, first to air inlet section, pass into inert gas, inert gas is discharged successively after air inlet section, conversion zone, spraying section, thereby by the air emptying in selenizing district.Because conversion zone is arranged between inlet zone and air inlet area, even due to conveyer belt and each intersegmental gap that exists, also can guarantee the air of emptying conversion zone, thereby improve the quality of conversion zone selenizing.When substrate enters conversion zone, should continue to pass into inert gas, selenylation reaction is carried out under protective gas, guarantee quality of forming film.
(5) after having reacted, by conveyer belt, substrate transfer is carried out to cooling zone cooling, then by its output; Can be cooling by input inert gas in cooling zone, also can be undertaken coolingly by water cooling plant is set, but should make the rate of temperature fall of cooling zone maintain 25 ℃/s--35 ℃/s, to enhance productivity.
Implementation procedure in invention is as follows:
First the substrate that is coated with preformed layer is positioned on conveyer belt, starts conveyer belt, by substrate transfer, to preheating zone, the temperature of preheating zone maintains 630 ℃--between 680 ℃, and make substrate Gai district insulation 15s-20s; Subsequently by conveyer belt by substrate transfer the spraying section to reaction zone, when substrate one end enters spraying section, by injection apparatus to spraying on it through the high activity selenium steam of cracking, when substrate moves, injection apparatus is incessantly to spraying selenium steam on it, until the substrate other end is about to leave spraying area, spray and just stop, this completed course of injection; Subsequently, whole backing material enters conversion zone, conveyer belt stop motion, and substrate, at this section of standing 2min-4min of class, carries out sufficient reacting; After having reacted, conveyer belt continues motion, thus absorbed layer is delivered to through air inlet area cooling zone carry out cooling, last cooling zone output absorbed layer again; Like this, just completed whole production process.
Above-mentioned execution mode is used for illustrative purposes only, and be not limitation of the present invention, the those of ordinary skill in relevant technologies field, without departing from the spirit and scope of the present invention, can also make various variations and modification, therefore all technical schemes that are equal to also should belong to category of the present invention.
Claims (7)
1. the selenizing method of thin-film solar cells CIGS absorbed layer, it comprises the following steps:
(1) prepare selenium steam;
(2) by conveyer belt by absorbed layer substrate transfer to preheating zone preheating;
(3) through the substrate transfer of preheating to the selenizing district with inert gas shielding, selenium steam is imported to selenizing district simultaneously, on mobile substrate, spray selenium steam;
(4) substrate that is coated with selenium reacts in selenizing district;
(5) after having reacted, by conveyer belt, substrate transfer is carried out to cooling zone cooling, then by its output.
2. selenizing method according to claim 1, is characterized in that: while preparing selenium steam, first selenium source is heated into selenium steam, then selenium steam is carried out to cracking, then the selenium steam of cracking is imported to selenizing district.
3. selenizing method according to claim 1, is characterized in that: preheating zone temperature maintains 630 ℃--680 ℃, and make substrate Gai district insulation 15s-20s.
4. selenizing method according to claim 1, is characterized in that: selenizing district is divided into spraying section, conversion zone and air inlet section successively, and substrate is when spraying section is mobile, to its upper injection selenium steam; After injection completes, substrate transfer to conversion zone reacts, and is delivered to cooling section after having reacted again.
5. selenizing method according to claim 4, is characterized in that: before substrate enters spraying area, first to air inlet section, pass into inert gas, inert gas is discharged successively after air inlet section, conversion zone, spraying section.
6. selenizing method according to claim 4, is characterized in that: the temperature in selenizing district maintains 830 ℃--880 ℃, substrate is at the standing 2min-4min of conversion zone.
7. selenizing method according to claim 1, is characterized in that: the rate of temperature fall of described cooling zone is 25 ℃/s--35 ℃/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620779.2A CN103606598A (en) | 2013-11-29 | 2013-11-29 | Method for selenizing CIGS absorbing layer of thin film solar cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310620779.2A CN103606598A (en) | 2013-11-29 | 2013-11-29 | Method for selenizing CIGS absorbing layer of thin film solar cell |
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| CN103606598A true CN103606598A (en) | 2014-02-26 |
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| CN201310620779.2A Pending CN103606598A (en) | 2013-11-29 | 2013-11-29 | Method for selenizing CIGS absorbing layer of thin film solar cell |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024870A (en) * | 2010-04-19 | 2011-04-20 | 福建欧德生光电科技有限公司 | System and method for manufacturing semiconductor thin film solar cell |
| CN102185024A (en) * | 2011-04-01 | 2011-09-14 | 湘潭大学 | Selenylation furnace for treating and preparing CIGS (Copper Indium Gallium Diselenide) solar cell absorbing layer and manufacturing method thereof |
-
2013
- 2013-11-29 CN CN201310620779.2A patent/CN103606598A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024870A (en) * | 2010-04-19 | 2011-04-20 | 福建欧德生光电科技有限公司 | System and method for manufacturing semiconductor thin film solar cell |
| CN102185024A (en) * | 2011-04-01 | 2011-09-14 | 湘潭大学 | Selenylation furnace for treating and preparing CIGS (Copper Indium Gallium Diselenide) solar cell absorbing layer and manufacturing method thereof |
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Application publication date: 20140226 |
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