CN111326602A - Annealing process, device and preparation method of copper indium gallium selenide solar thin film - Google Patents
Annealing process, device and preparation method of copper indium gallium selenide solar thin film Download PDFInfo
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- 238000000137 annealing Methods 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 98
- 239000010409 thin film Substances 0.000 title claims abstract description 72
- 230000008569 process Effects 0.000 title claims abstract description 40
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 75
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 52
- 239000011669 selenium Substances 0.000 claims abstract description 52
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000010549 co-Evaporation Methods 0.000 claims abstract description 37
- VZZSRKCQPCSMRS-UHFFFAOYSA-N dipotassium;selenium(2-) Chemical compound [K+].[K+].[Se-2] VZZSRKCQPCSMRS-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims description 112
- 230000008020 evaporation Effects 0.000 claims description 104
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 57
- 238000010438 heat treatment Methods 0.000 claims description 44
- 239000010408 film Substances 0.000 claims description 43
- 229910052738 indium Inorganic materials 0.000 claims description 31
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 31
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052786 argon Inorganic materials 0.000 claims description 29
- 229910052733 gallium Inorganic materials 0.000 claims description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 28
- 229910052802 copper Inorganic materials 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 28
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- 230000008021 deposition Effects 0.000 claims description 15
- 239000007888 film coating Substances 0.000 claims description 6
- 238000009501 film coating Methods 0.000 claims description 6
- 239000013077 target material Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical group [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- -1 on one hand Chemical compound 0.000 abstract description 5
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 5
- 238000010248 power generation Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000013589 supplement Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 19
- 230000005540 biological transmission Effects 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- IRPLSAGFWHCJIQ-UHFFFAOYSA-N selanylidenecopper Chemical compound [Se]=[Cu] IRPLSAGFWHCJIQ-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000005361 soda-lime glass Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000807 Ga alloy Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 description 1
- 238000001883 metal evaporation Methods 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
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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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
- H01L31/0323—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 characterised by the doping material
-
- 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
Abstract
The invention belongs to the technical field of preparation of copper indium gallium selenide solar thin film batteries, and particularly relates to an annealing process for preparing a copper indium gallium selenide solar thin film, a device used by the annealing process and a preparation method of the solar thin film. The annealing process comprises the step of depositing potassium selenide on the substrate plated with the CIGS thin film in a co-evaporation mode in an inert gas atmosphere when the substrate plated with the CIGS thin film is subjected to annealing treatment. The annealing process can improve the conversion rate of selenium element, and the CIGS thin film prepared by the annealing process provided by the invention has high forbidden bandwidth value; by adding the potassium selenide, on one hand, selenium element can be supplemented, the proportion of four elements in the CIGS thin film is ensured, and meanwhile, potassium ions can be added to supplement active metal ions, so that the carrier density and the power generation conversion rate of the thin film are improved, the electron mobility is improved, and the resistivity is reduced.
Description
Technical Field
The invention belongs to the technical field of preparation of copper indium gallium selenide solar thin film batteries, and particularly relates to an annealing process for preparing a copper indium gallium selenide solar thin film, a device used by the annealing process and a preparation method of the solar thin film.
Background
With the rapid increase of world energy demand, traditional petrochemical energy sources cannot meet our energy demand more and more. Solar energy is one of the most potential new energy sources with the advantages of cleanness, no pollution and the like, and meanwhile, solar cells enter the golden period of rapid development.
The copper indium gallium selenide thin film Cell (CIGS) has the advantages of few manufacturing procedures, low relative cost, stable performance, strong radiation resistance, high photoelectric conversion efficiency and the like, and becomes one of the research hotspots of the solar cell.
At present, two methods for producing and preparing CIGS thin films mainly comprise a selenization method after sputtering and a co-evaporation method, wherein the co-evaporation method has the advantage that the reaction process is easy to accurately control, and the laboratory photoelectric conversion efficiency of the CIGS thin film solar cell prepared by using the process is over 20 percent; meanwhile, many companies and research institutions establish megawatt production lines of CIGS thin film cell modules by taking a co-evaporation process as a main technical route, the average efficiency of the cell modules is mostly more than 12%, and therefore, the co-evaporation method is considered as the best choice for preparing the high-efficiency CIGS solar cell.
The CIGS thin film is formed by reacting four elements of copper, indium, gallium and selenium on a substrate in a co-evaporation environment, wherein the copper, the indium and the gallium account for about 50% of the components of a film layer, the selenium accounts for about 50% of the components of the film layer, and the co-evaporation process chamber ensures the thickness and the component proportion of the film layer, so that the residence time of the substrate in the chamber is too short, and the CIGS thin film in the co-evaporation chamber cannot be fully annealed and grown. In order to fully optimize the crystal structure, the CIGS film needs to be subjected to an annealing chamber to fully grow the crystals, but in the existing annealing technology, the CIGS film is recrystallized, selenium is consumed in the recrystallization process, active metal ions are lacked as carriers, the conversion rate of the selenium is limited, and the change of the composition of the CIGS film is caused. In the prior art, chinese patent document CN 105789371a discloses a method for doping potassium element in a copper indium gallium selenide thin-film solar cell, which is to prepare a copper indium gallium selenide thin film by a co-evaporation three-step method, after the process of preparing a copper indium gallium selenide absorption layer by the three-step method is finished, a selenium evaporation source is not closed, other metal evaporation sources are closed, and an evaporation source containing potassium fluoride element is heated.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that active metal ions are lacked in the annealing process of preparing the CIGS thin film by a co-evaporation method in the prior art, the conversion rate of selenium element in the CIGS thin film is limited and the like, so that the annealing process in the preparation of the CIGS solar thin film is provided.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides an annealing process of a CIGS solar film, which comprises the following steps of depositing potassium selenide on a CIGS film plated substrate in a co-evaporation mode in an inert gas atmosphere when the CIGS film plated substrate is annealed.
The inert atmosphere is helium, neon, krypton or argon; preferably, the inert gas is argon.
The annealing temperature is 400-500 ℃, and the annealing time is 30-60 min.
Preferably, the annealing temperature is 400-500 ℃, and the annealing time is 50-60 min.
The heating power of the potassium selenide co-evaporation is 1000-1500w, and the time is 20-40 min.
Preferably, the heating power of the potassium selenide co-evaporation is 1000-1500w, and the time is 25-35 min.
The invention also provides a preparation method of the CIGS solar film, which comprises the following steps,
preparing a substrate plated with a CIGS film;
and annealing by adopting the annealing process to obtain the copper indium gallium selenide solar film.
The CIGS thin film is prepared by combining co-evaporation and magnetron sputtering, a co-evaporation method or a selenization method after magnetron sputtering.
The method for preparing the CIGS film by combining the co-evaporation and the magnetron sputtering comprises the following steps:
taking three elements of copper, indium and gallium as evaporation sources, and according to the moving direction of the substrate, performing evaporation coating on the substrate by taking the arrangement sequence of the evaporation sources that the two elements of gallium and indium are in front, copper is in the middle and the two elements of gallium and indium are alternately finished, and performing magnetron sputtering on the substrate by taking a selenium target material as a magnetron sputtering target to obtain the coated substrate; and annealing the coated substrate to obtain the CIGS solar film.
The selenium target is a mixture of selenium and copper selenide.
The magnetron sputtering power of the selenium target is 5-10 kw; the distance between the selenium target and the substrate is 1-1.5 m; the deposition rate of the selenium element is 1-5A/S.
The evaporation sources are arranged at equal intervals, and the distance between the evaporation sources is 30-50 cm; the distance between the evaporation source and the substrate is 1.2-1.5 m.
The heating power of the gallium evaporation source is 0.8-1 kw; the heating power of the copper evaporation source is 2-3 kw; the heating power of the indium evaporation source is 0.8-1 kw;
the deposition rate of the gallium element is 1-3A/S; the deposition rate of the copper element is 1-4A/S; the deposition rate of the indium element is 1-3A/S.
The temperature of the substrate is 500-600 ℃; the moving speed of the substrate is 10-50 cm/min.
In addition, the invention also provides an annealing device of the CIGS solar film, which comprises,
an annealing chamber for annealing the CIGS solar film, comprising,
the conveying device is arranged in the annealing chamber and used for bearing and moving the substrate;
the evaporation source is used for evaporating potassium selenide and is arranged in a heater, and the heater is hermetically connected with the film coating chamber;
and the inert gas inlet is arranged at the bottom of the annealing chamber and on two sides of the evaporation source.
The invention also provides a coating device for preparing the CIGS solar film by combining a co-evaporation method and a magnetron sputtering method, which comprises,
the coating chamber is used for realizing magnetron sputtering and evaporation coating of the substrate;
the film coating chamber comprises a film coating chamber,
the conveying device is arranged in the coating chamber and used for bearing and moving the substrate;
the distribution device is used for containing the target and distributing sputtered target elements and is arranged opposite to the conveying device, and one side of the distribution device, which faces the conveying device, is provided with a plurality of nozzles;
the evaporation source is used for providing metal elements required by evaporation coating, the evaporation source is placed in a heater, and the heater is connected with the coating chamber through a flange.
The technical scheme of the invention has the following advantages:
1. the annealing process in the preparation method of the CIGS solar film comprises the following steps of depositing potassium selenide on the substrate plated with the CIGS film in a co-evaporation mode in an inert gas atmosphere when the substrate plated with the CIGS film is annealed. Because the film coating chamber is communicated with the annealing chamber, impurities generated by the reaction of the copper indium gallium selenium in the film coating chamber can be doped in the annealing chamber, and because the inert gas inlet is close to the potassium selenide evaporation source, the potassium selenide can be coated by the inert gas in the process from the evaporation source to the substrate, the influence of the impurities is not easily caused, the excessive selenium element is prevented from being consumed, the potassium selenide directly reaches the substrate, and the conversion rate of the selenium element is further improved; meanwhile, the argon can conduct heat at high temperature, the heat can be uniformly dispersed on the substrate, crystals can fully grow, small particles are gradually polymerized to form large particles, the forbidden band width is distributed in a clear limit, the crystals of the film layer are optimized, the power generation conversion rate is improved, and the annealing effect is guaranteed. In the annealing treatment, selenium element is easy to react with other metal elements and is consumed, and potassium selenide is added in the process, so that on one hand, the selenium element can be supplemented, the proportion of four elements in the CIGS thin film is ensured, on the other hand, active metal potassium ions can be supplemented by adding the potassium selenide, and the potassium ions are enriched on the upper layer of the CIGS thin film, so that the carrier density and the power generation conversion rate of the thin film can be improved, the electrical property of the thin film is improved, and the resistivity is reduced; after the potassium ions are added, the buffering depth of the CIGS thin film and the CdS of the solar cell buffer layer is reduced when the solar cell is prepared, the CIGS thin film is prevented from being excessively corroded by the buffer layer, and the thin wall is enabled to be converted into the effective depth.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a front view of a coating chamber for preparing a CIGS solar film by combining a co-evaporation method and a magnetron sputtering method;
FIG. 2 is a top view of a coating chamber for preparing a CIGS solar film by combining a co-evaporation method and a magnetron sputtering method according to the invention;
FIG. 3 is a top view of an annealing chamber for preparing CIGS solar thin films according to the present invention;
FIG. 4 is the upper cover of the annealing chamber for preparing CIGS solar thin film according to the present invention;
the reference numbers are as follows:
1-substrate, 2-selenium distribution device, 3-nozzle, 4-evaporation source and 5-selenium target material; 6-a transmission device; 7-argon gas outlet; 8-coil type heating wire.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a method for preparing a copper indium gallium selenide solar film by combining a co-evaporation method and magnetron sputtering and an annealing process, and the method specifically comprises the following steps:
in a CIGS coating chamber, soda-lime glass is used as a substrate 1 and is installed on a transmission device 6, the transmission device 6 is arranged above a chamber, a heating source is arranged above the glass substrate 1, the temperature is 600 ℃, the transmission device 6 starts to transmit at the speed of 30cm/min, the chamber is sequentially provided with a gallium evaporation source, an indium evaporation source, a copper evaporation source, a gallium evaporation source and an indium evaporation source from left to right, the distance between the evaporation sources is 30cm, the distance between the evaporation sources and the substrate 1 is 1.2m, the evaporation sources are respectively arranged at the bottom of the chamber and at two sides of a selenium distribution device 2, the heating power of the gallium evaporation source is 900w, the heating power of the copper evaporation source is 2500w, the heating power of the indium evaporation source is 900w, and the deposition rate; the deposition rate of the copper element is 3A/S; the deposition rate of the indium element is 2A/S; the method comprises the steps that a selenium target 5 is arranged in the middle of the bottom of a chamber, the sputtering power is 10kw, the deposition rate of selenium is 5A/S, three metal elements of copper, indium and gallium are electroplated on a glass substrate 1 through a co-evaporation method, the gradient formed by the copper element is located in the middle of the gradient of a CIGS thin film, meanwhile, argon is introduced into a selenium distribution device 2, the target 5 is bombarded through a magnetron sputtering method, selenium and copper selenide are sprayed out from a nozzle 3, from bottom to top, cloud-state substances are formed, a high-temperature-resistant distribution device is used for assisting, under the action of high negative pressure outside a distributor in a high-vacuum chamber, mixed cloud formed by the selenium and the copper selenide is sprayed to the glass substrate 1, and the distance between the nozzles 3 is 60 cm; and then conveying the CIGS thin film substrate to an annealing chamber, arranging a roll-type heating wire 8 above the annealing chamber, continuously heating, keeping the temperature of the substrate at 500 ℃, arranging argon gas outlets 7 at two sides of a potassium selenide evaporation source, introducing argon gas into the argon gas outlets 7, diffusing the potassium selenide into the annealing chamber by adopting an evaporation method under the argon gas atmosphere, and depositing the potassium selenide mixed with the argon gas on the CIGS thin film substrate 1 to obtain the CIGS solar thin film, wherein the heating power of the potassium selenide evaporation source is 1000w, the evaporation time is 40min, the evaporation rate is tested by a quartz crystal oscillator, the annealing temperature of the annealing chamber is 500 ℃, and the annealing time is 60 min.
The embodiment also provides a device, which comprises a coating device and an annealing device for preparing the CIGS thin film by combining a co-evaporation method and a magnetron sputtering method, and the device comprises the following specific steps:
the coating device comprises a coating chamber for realizing magnetron sputtering and evaporation coating of the substrate; the coating chamber comprises a transmission device 6, a selenium distribution device 2, a nozzle 3, an evaporation source and a selenium target 5; the distribution device is used for containing a target 5 and distributing sputtered target elements, is arranged opposite to the conveying device 6, and a plurality of nozzles 3 are arranged on one side, facing the conveying device, of the distribution device 2; the evaporation source is used for providing metal elements required by evaporation coating, the evaporation source is placed in a heater, and the heater is connected with the coating chamber through a flange;
the annealing device comprises an annealing chamber for annealing the CIGS thin film; the annealing chamber comprises a transmission device 6, an evaporation source, an argon gas outlet 7 and a coiled heating wire 8; the transmission device is used for bearing and moving the substrate; the evaporation source is used for evaporating potassium selenide; the argon gas outlets are arranged at two sides of the potassium selenide evaporation source; the rolled heating wire is arranged above the annealing chamber.
Example 2
The embodiment provides a method for preparing a copper indium gallium selenide solar film by a co-evaporation method and an annealing process, and the method specifically comprises the following steps:
in a CIGS coating chamber, soda-lime glass is used as a substrate and is installed on a transmission device, the temperature of a heating source above the glass substrate is set to be 600 ℃, a selenium evaporation source, a gallium evaporation source, an indium evaporation source, a selenium evaporation source, a copper evaporation source and a selenium evaporation source are sequentially arranged in the chamber from left to right, the heating power of the copper and gallium evaporation sources is 900w, the heating power of the copper evaporation source is 2500w, the heating power of the indium evaporation source is 900w, the heating power of the selenium evaporation source is 1000w, four elements are deposited on the glass substrate by a co-evaporation method, then the CIGS film substrate is transmitted to an annealing chamber, a rolled heating wire 8 is arranged above the annealing chamber for continuous heating, the temperature of the substrate 1 is kept to be 450 ℃, an argon gas outlet 7 is arranged at two sides of a potassium selenide evaporation source, argon gas is introduced into an argon gas inlet 7, potassium, and depositing the potassium selenide mixed with argon on the CIGS thin film substrate 1 to obtain the CIGS solar thin film, wherein the heating power of a potassium selenide evaporation source is 1500w, the evaporation time is 30min, the evaporation rate is tested by a quartz crystal oscillator, the annealing temperature of an annealing chamber is 450 ℃, and the annealing time is 30 min.
Example 3
The embodiment provides a method for preparing a copper indium gallium selenide solar film by a selenization method after magnetron sputtering and an annealing process, and the method specifically comprises the following steps:
in a CIGS coating chamber, soda-lime glass is used as a substrate, the temperature of the glass substrate is 600 ℃, argon is introduced into a magnetron sputtering chamber, the target material is pre-sputtered for 10min, impurity particles adsorbed on the surface of the target material are removed, a copper-gallium alloy layer is sputtered on the substrate through a copper-gallium alloy target, and then an indium metal layer is sputtered through an indium target to form a first copper-indium-gallium-selenium prefabricated layer; and then forming a second prefabricated layer on the first prefabricated layer by magnetron sputtering of a copper target, an indium target and a gallium target, selenizing, depositing selenium on the second prefabricated layer, then conveying the CIGS thin film to an annealing chamber, arranging a spiral heating wire 8 above the annealing chamber, continuously heating, keeping the temperature of the substrate 1 at 500 ℃, arranging argon gas outlets 7 at two sides of a potassium selenide evaporation source, introducing argon gas into the argon gas outlets 7, diffusing potassium selenide into the annealing chamber by adopting an evaporation method under the argon atmosphere, and obtaining the CIGS solar thin film on the CIGS thin film substrate 1 on which the potassium selenide mixed with the argon is deposited, wherein the heating power of the potassium selenide evaporation source is 1200w, the evaporation time is 25min, the evaporation rate is tested by a quartz crystal oscillator, and the annealing temperature of the annealing chamber is 500 ℃ and the annealing time is 55 min.
Example 4
The embodiment provides a method for preparing a copper indium gallium selenide solar film by combining a co-evaporation method and magnetron sputtering and an annealing process, and the method specifically comprises the following steps:
in a CIGS coating chamber, quartz glass is used as a substrate 1 and is installed on a transmission device 6, the transmission device 6 is arranged above a chamber, a heating source is arranged above the glass substrate 1, the temperature is 600 ℃, the transmission device 6 starts to transmit at the speed of 50cm/min, the chamber is sequentially provided with a gallium evaporation source, an indium evaporation source, a copper evaporation source, a gallium evaporation source, an indium evaporation source, a gallium evaporation source and an indium evaporation source from left to right, the distance between the evaporation sources is 50cm, the distance between the evaporation sources and the substrate 1 is 1.5m, the evaporation sources are respectively arranged at the bottom of the chamber and at two sides of a selenium distribution device 2, the heating power of the gallium evaporation source is 1000w, the heating power of the copper evaporation source is 3000w, the heating power of the indium evaporation source; the deposition rate of the copper element is 4A/S; the deposition rate of the indium element is 3A/S; the method comprises the steps that a selenium target 5 is arranged in the middle of the bottom of a chamber, the sputtering power is 5kw, the deposition rate of selenium is 1A/S, three metal elements of copper indium gallium are electroplated on a glass substrate 1 through a co-evaporation method, the gradient formed by the copper elements is located in the middle of the gradient of a CIGS thin film, meanwhile, argon is introduced into a selenium distribution device, the target 5 is bombarded through a magnetron sputtering method, selenium and copper selenide are sprayed out from a nozzle 3, a cloud-state substance is formed from bottom to top, a high-temperature-resistant distribution device is used for assisting, under the action of high negative pressure outside a distributor in a high-vacuum chamber, a mixed cloud formed by the selenium and the copper selenide is sprayed to the glass substrate 1, and the distance between the nozzles 3 is 95 cm; and then, conveying the CIGS thin film substrate 1 to an annealing chamber, arranging a roll-type heating wire 8 above the annealing chamber, continuously heating, keeping the temperature of the substrate at 400 ℃, arranging argon gas outlets 7 at two sides of a potassium selenide evaporation source, introducing argon gas into the argon gas outlets 7, diffusing the potassium selenide into the annealing chamber by adopting an evaporation method under the argon gas atmosphere, and depositing the potassium selenide mixed with the argon gas on the CIGS thin film substrate 1 to obtain the CIGS solar thin film, wherein the heating power of the potassium selenide evaporation source is 1200w, the evaporation time is 20min, the evaporation rate is tested by a quartz crystal oscillator, the annealing temperature of the annealing chamber is 400 ℃, and the annealing time is 50 min.
Comparative example 1
The comparative example provides a method for preparing a copper indium gallium selenide solar film by combining co-evaporation and magnetron sputtering and an annealing process, and the method specifically comprises the following steps:
in a CIGS coating chamber, soda-lime glass is used as a substrate and is installed on a transmission device, the transmission device is arranged above a chamber, a heating source is arranged above the glass substrate, the temperature is 600 ℃, the transmission device starts to transmit at the speed of 30cm/min, the chamber is sequentially provided with a gallium evaporation source, an indium evaporation source, a copper evaporation source, a gallium evaporation source and an indium evaporation source from left to right, the distance between the gallium evaporation sources and the substrate is 30cm, the evaporation sources are 1.2m away from the substrate, the evaporation sources are respectively arranged at the bottom of the chamber and at two sides of a selenium distribution device, the heating power of the gallium evaporation source is 900w, the heating power of the copper evaporation source is 2500w, the heating power of the indium evaporation source is 900w, and; the deposition rate of the copper element is 3A/S; the deposition rate of the indium element is 2A/S; the method comprises the steps that a selenium target is arranged in the middle of the bottom of a chamber, the sputtering power is 10kw, the deposition rate of selenium is 5A/S, three metal elements of copper indium gallium are electroplated on a glass substrate through a co-evaporation method, the gradient formed by the copper element is located in the middle of the gradient of a CIGS thin film, meanwhile, argon is introduced into a selenium distribution device, the target is bombarded through a magnetron sputtering method, selenium and copper selenide are sprayed out of nozzles, cloud-state substances are formed from bottom to top, a high-temperature-resistant distribution device is used for assisting, under the action of high negative pressure outside a distributor, a mixed cloud formed by the selenium and the copper selenide is sprayed to the glass substrate in a high vacuum chamber, the distance between the nozzles is 60cm, then the CIGS thin film substrate is conveyed to an annealing chamber to be annealed, and the CIGS solar thin film is obtained, the annealing temperature is 500 ℃, and the.
Comparative example 2
The comparative example provides a method for preparing a copper indium gallium selenide solar film by co-evaporation and an annealing process, and the method comprises the following specific steps:
in a CIGS coating chamber, soda-lime glass is used as a substrate and is installed on a transmission device, the temperature of a heating source above the glass substrate is set to be 600 ℃, a selenium evaporation source, a gallium evaporation source, an indium evaporation source, a selenium evaporation source, a copper evaporation source and a selenium evaporation source are sequentially arranged in the chamber from left to right, the heating power of the copper and gallium evaporation sources is 900w, the heating power of the copper evaporation source is 2500w, the heating power of the indium evaporation source is 900w, the heating power of the selenium evaporation source is 1000w, four elements are deposited on the glass substrate by a co-evaporation method, then the CIGS film substrate is transmitted to an annealing chamber to be annealed to obtain the CIGS solar film, wherein the annealing temperature is 500 ℃, and the annealing time is 60.
Test examples
The CIGS thin films prepared in the examples 1-4 and the comparative examples 1-2 are subjected to performance tests, and the performance test results are shown in Table 1; the CIGS thin film is obtained by testing the resistivity, the mobility and the carrier concentration through an HL5500Hall effect testing system at normal temperature by adopting a Van der Pauw method; the forbidden band width is measured by a spectrometer.
In the embodiment 1 and the embodiment 4, the CIGS solar thin film is obtained by annealing through the annealing process provided by the invention after the CIGS thin film is prepared by combining the co-evaporation method and the magnetron sputtering method.
In embodiment 2, a CIGS thin film is prepared by a co-evaporation method, and is annealed by the annealing process provided by the present invention, so that a CIGS solar thin film is obtained.
In embodiment 3, a CIGS thin film is prepared by a magnetron sputtering method, and is annealed by the annealing process provided by the present invention, so that a CIGS solar thin film is obtained.
Table 1 results of performance test of CIGS thin films prepared in examples 1 to 4 and comparative examples 1 to 2
Example 1 differs from comparative example 1 and example 2 from comparative example 2 in the annealing process, and comparative example 1 and comparative example 2 employ a conventional annealing process. As can be seen from table 1, compared with comparative example 1, example 1 and example 2 are compared with comparative example 2, which illustrate that the annealing process provided by the present invention, that is, when the annealing process is performed, potassium selenide is deposited on the substrate plated with the CIGS thin film in a manner of co-evaporating potassium selenide under an inert gas atmosphere, so that the conversion rate of selenium element can be increased, and meanwhile, the forbidden bandwidth value and the power generation conversion rate of the CIGS thin film prepared by the annealing process provided by the present invention are higher than those of the CIGS thin films of comparative examples 1 and 2. In the invention, by adding potassium selenide, on one hand, selenium element can be supplemented to ensure the proportion of four elements in the CIGS film, and simultaneously potassium ions can be added to supplement active metal ions, thereby improving the carrier density and the power generation conversion rate of the film, improving the electron mobility and reducing the resistivity.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The annealing process of the CIGS solar thin film is characterized by comprising the following steps of depositing potassium selenide on the CIGS thin film plated substrate in a co-evaporation mode in an inert gas atmosphere when the CIGS thin film plated substrate is annealed.
2. The CIGS solar film annealing process of claim 1, wherein the inert atmosphere is helium, neon, krypton, or argon.
3. The annealing process of CIGS solar thin film as claimed in claim 1 or 2, wherein the annealing temperature is 400-500 ℃ and the annealing time is 30-60 min.
4. The annealing process of CIGS solar thin film as claimed in claim 3, wherein the annealing temperature is 400-500 ℃ and the annealing time is 50-60 min.
5. The annealing process of CIGS solar thin film as claimed in claim 1, wherein the heating power of the potassium selenide is 1000-1500w, and the evaporation time is 20-40 min;
the deposition rate of the potassium selenide is 2-4A/S.
6. The annealing process of CIGS solar thin film as claimed in claim 5, wherein the heating power of the potassium selenide is 1000-1500w for 25-35 min.
7. A preparation method of a copper indium gallium selenide solar film is characterized by comprising the following steps,
preparing a substrate plated with a CIGS film;
annealing treatment is carried out by adopting the annealing process of any one of claims 1 to 6, and the copper indium gallium selenide solar thin film is obtained.
8. The method for preparing the CIGS solar film according to claim 7, wherein the CIGS film is prepared by a co-evaporation method, a selenization method after magnetron sputtering or a method combining co-evaporation and magnetron sputtering.
9. The method for preparing the CIGS solar film according to claim 8, wherein the method for preparing the CIGS film by combining the co-evaporation and the magnetron sputtering comprises the following steps:
taking three elements of copper, indium and gallium as evaporation sources, and according to the moving direction of the substrate, performing evaporation coating on the substrate by taking the arrangement sequence of the evaporation sources that the two elements of gallium and indium are in front, copper is in the middle and the two elements of gallium and indium are alternately finished, and performing magnetron sputtering on the substrate by taking a selenium target material as a magnetron sputtering target to obtain the coated substrate; and annealing the coated substrate to obtain the CIGS solar film.
10. An annealing device of a CIGS solar film is characterized by comprising,
the annealing chamber is used for annealing the copper indium gallium selenide solar thin film;
the conveying device is arranged in the annealing chamber and used for bearing and moving the substrate;
the evaporation source is used for evaporating potassium selenide and is arranged in a heater, and the heater is hermetically connected with the film coating chamber;
and the inert gas inlet is arranged at the bottom of the annealing chamber and on two sides of the evaporation source.
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