CN111416018A - Selenizing device and method for copper-zinc-tin-sulfur thin film material - Google Patents
Selenizing device and method for copper-zinc-tin-sulfur thin film material Download PDFInfo
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- CN111416018A CN111416018A CN202010236832.9A CN202010236832A CN111416018A CN 111416018 A CN111416018 A CN 111416018A CN 202010236832 A CN202010236832 A CN 202010236832A CN 111416018 A CN111416018 A CN 111416018A
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- 239000010409 thin film Substances 0.000 title claims abstract description 41
- 239000000463 material Substances 0.000 title claims abstract description 36
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 84
- 239000011669 selenium Substances 0.000 claims abstract description 84
- 239000007789 gas Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 239000010408 film Substances 0.000 claims abstract description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000005086 pumping Methods 0.000 claims abstract description 5
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 230000001502 supplementing effect Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 229910002804 graphite Inorganic materials 0.000 claims description 39
- 239000010439 graphite Substances 0.000 claims description 39
- 239000010453 quartz Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 15
- 238000012544 monitoring process Methods 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000004891 communication Methods 0.000 claims 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000004528 spin coating Methods 0.000 description 4
- 239000011135 tin Substances 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- DLLMHEDYJQACRM-UHFFFAOYSA-N 2-(carboxymethyldisulfanyl)acetic acid Chemical compound OC(=O)CSSCC(O)=O DLLMHEDYJQACRM-UHFFFAOYSA-N 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910003310 Ni-Al Inorganic materials 0.000 description 2
- PDYXSJSAMVACOH-UHFFFAOYSA-N [Cu].[Zn].[Sn] Chemical compound [Cu].[Zn].[Sn] PDYXSJSAMVACOH-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910000058 selane Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 1
- LBSAHBJMEHMJTN-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Zn].[Zn] LBSAHBJMEHMJTN-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002341 toxic gas Substances 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
-
- 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
- H01L31/0326—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising AIBIICIVDVI kesterite compounds, e.g. Cu2ZnSnSe4, Cu2ZnSnS4
-
- 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)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a selenizing device for a copper-zinc-tin-sulfur thin film material. The invention also provides a selenizing method of the copper-zinc-tin-sulfur thin film material, which comprises the following steps: placing a selenium source in an annular container of a selenium source area, and simultaneously placing a prefabricated film of a copper-zinc-tin-sulfur thin film material to be selenized in a selenization reaction area; then, connecting a heating wire and a thermocouple wire, and sealing the cabin body; and then, pumping air in the cabin body completely by using a vacuum pump, supplementing high-pressure nitrogen into the cabin body, and finally controlling the temperature and the pressure in the cabin body by using a computer control system, so that selenium steam formed by heating a selenium source is cracked into micromolecular selenium steam through a gas treatment area, then enters a selenization reaction area downwards and performs a selenization reaction with the prefabricated film, and further selenizing the prefabricated film is realized. The device and the method can accurately control the time and the concentration of the selenium steam reaching the surface of the prefabricated film, thereby obtaining the high-quality copper-zinc-tin-sulfur-selenium crystal.
Description
Technical Field
The invention belongs to the field of semiconductor photoelectric material preparation. In particular, the invention relates to a selenizing device and a selenizing method for a copper-zinc-tin-sulfur thin film material.
Background
In the field of solar cells, copper zinc tin sulfur selenium solar cells have the advantages of high light absorption coefficient and cheap and abundant raw materials, and are gradually paid attention by researchers. The preparation of the copper zinc tin sulfur selenium active layer generally adopts a post-selenization method to carry out selenization treatment on the copper zinc tin sulfur prefabricated film to obtain the copper zinc tin sulfur selenium crystal. The selenizing process can adopt hydrogen selenide with stronger activity as a selenium source, but the safety is poorer. Hydrogen selenide belongs to a highly toxic gas, is flammable and explosive, has poor safety and is expensive. The method for preparing the copper-zinc-tin-sulfur-selenium thin-film solar cell material by adopting elemental selenium as a selenium source to carry out a selenization reaction is more and more common, but the elemental selenium is solid at normal temperature, and generally needs to form selenium steam at a high temperature to participate in the reaction, so that higher requirements are provided for the generation of the selenium steam, the control of the concentration of the selenium steam and the recovery of the selenium.
Therefore, a method capable of controlling the concentration of selenium vapor well and forming high-quality copper zinc tin sulfur selenium crystals is urgently needed.
Disclosure of Invention
The invention aims to provide a selenizing device for a copper-zinc-tin-sulfur thin film material, which can well control the concentration of selenium steam and the pressure during the selenizing reaction. The invention also aims to provide a selenizing method of the copper zinc tin sulfide thin film material, which can form high-quality copper zinc tin sulfide selenium crystals.
The above object of the present invention is achieved by the following means.
In the context of the present invention, certain directional terms, such as "inner," "outer," "above," "below," and other directional terms, used in describing the present invention, are to be understood as having their ordinary meaning and refer to those directions as they would normally be referred to in the drawings. Unless otherwise indicated, the directional terms described herein are generally in accordance with conventional directions as understood by those skilled in the art.
In the context of the present invention, the term "copper zinc tin sulfide thin film material" refers to a material containing the elements copper, zinc, tin, sulfur.
On one hand, the invention provides a copper zinc tin sulfur film material selenizing device 1, which comprises a cabin body 11, a graphite container 12, an infrared heating jacket 13 and a computer control system 14;
the cabin 11 is a pressure-bearing closed cabin, an electrode flange 115 is arranged on the cabin, and a graphite container 12 and an infrared heating jacket 13 are arranged in the cabin;
the graphite container 12 is vertically arranged, and the graphite container 12 comprises a selenium source region 121 positioned at the upper section, a gas treatment region 122 positioned at the middle section and a selenization reaction region 123 positioned at the lower section; the selenium source region 121 and the gas processing region 122 and the selenization reaction region 123 are hermetically connected with each other; thermocouples 127 are respectively arranged in the side walls of the upper section, the middle section and the lower section of the graphite container 12;
the infrared heating jacket 13 is arranged around the graphite container 12, and the infrared heating jacket 13 includes three sections corresponding to the selenium source region 121, the gas processing region 122 and the selenization reaction region 123, respectively; three sections of the infrared heating jacket 13 are respectively provided with a heating wire 131;
the electrode flange 115 is used to connect the thermocouples 127 and heater wires 131 inside the enclosure 11 to a temperature control system 1151 outside the enclosure 11;
the computerized control system 14 is coupled to the temperature control system 1151 and is configured to control the temperature of the various zones within the enclosure 11.
Preferably, in the selenizing apparatus 1 of a copper-zinc-tin-sulfur thin film material of the present invention, the chamber 11 is further provided with a controllable inlet valve 113, a pressure gauge 114, a pipeline cold trap 116, and a controllable outlet valve 1161;
the controllable air inlet valve 113 is connected with high-pressure nitrogen 1131;
the pressure gauge 114 is used for monitoring the pressure in the cabin 11 in real time;
the pipeline cold trap 116 is used for connecting the cabin 11 and the controllable gas outlet valve 1161; the controllable air outlet valve 1161 is connected with a vacuum pump 1162.
Preferably, in the selenizing apparatus 1 of the copper-zinc-tin-sulfur thin film material of the present invention, the controllable inlet valve 113, the pressure gauge 114 and the controllable outlet valve 1161 are connected to the computer control system 14, so as to realize real-time control of the pressure inside the chamber 11.
Preferably, in the selenizing apparatus 1 of a copper-zinc-tin-sulfur thin film material according to the present invention, the chamber 11 is further provided with an evacuation valve 111 and a safety valve 112.
Preferably, in the selenizing apparatus 1 of the copper-zinc-tin-sulfur thin film material of the present invention, the lower section of the graphite container 12 is provided with a gas guiding hole 124, and the gas guiding hole 124 is used for communicating the chamber 11 and the selenizing reaction zone 123.
Preferably, in the selenization apparatus 1 of the zns thin film material of the present invention, the top of the selenium source region 121 is sealed, and the upper end of the pipe constituting the gas processing region 122 forms a protrusion 128 communicating with the selenium source region 121 with respect to the bottom of the selenium source region 121.
Preferably, in the selenizing apparatus 1 of the copper-zinc-tin-sulfur thin film material of the present invention, a quartz liner 129 is disposed on an inner wall of the graphite container 12, and the quartz liner 129 is used for preventing selenium from permeating towards a wall of the graphite container 12.
Preferably, in the selenization apparatus 1 of the copper-zinc-tin-sulfur thin film material of the present invention, the selenium source region 121 and the gas processing region 122, and the gas processing region 122 and the selenization reaction region 123 are hermetically connected to each other by a thread and a gasket.
Preferably, in the selenizing apparatus 1 for a copper-zinc-tin-sulfur thin film material of the present invention, the chamber 11 can withstand 0.01Pa-1 × 106Pressure of Pa.
On the other hand, the invention provides a selenizing method of a copper-zinc-tin-sulfur thin film material, which uses the selenizing device (1) provided by the invention and comprises the following steps:
placing a selenium source in an annular container of a selenium source area, and simultaneously placing a prefabricated film of a copper-zinc-tin-sulfur thin film material to be selenized in a selenization reaction area; then, connecting a heating wire and a thermocouple wire, and sealing the cabin body; and then, pumping air in the cabin body completely by using a vacuum pump, supplementing high-pressure nitrogen into the cabin body, and finally controlling the temperature and the pressure in the cabin body by using a computer control system, so that selenium steam formed by heating a selenium source is cracked into micromolecular selenium steam through a gas treatment area, then enters a selenization reaction area downwards and performs a selenization reaction with the prefabricated film, and further selenizing the prefabricated film is realized.
Preferably, in the method of the present invention, the controlling the temperature inside the cabin body by the computer control system is controlling the temperature inside the cabin body according to the following conditions:
the heating rate of the selenium source region is 100 ℃/min-1200 ℃/min, and the temperature is maintained for 10-40min after being heated to 200 ℃ and 1300 ℃;
the temperature rise rate of the gas treatment area is 100-1200 ℃/min, and the temperature is maintained for 10-40min after rising to 200-1300 ℃;
the temperature rise rate of the selenization reaction zone is 100 ℃/min-1200 ℃/min, and the temperature is maintained for 2-40min after being raised to 200 ℃ and 1300 ℃.
Preferably, in the method of the present invention, the gas treatment area starts to be heated, and the selenium source area is heated 0-10min after the gas treatment area starts to be heated; and heating the selenization reaction zone 0-20min after the gas treatment zone starts to be heated.
Preferably, in the method of the present invention, the controlling the pressure inside the chamber by the computer control system is controlling the pressure inside the chamber according to the following conditions:
the pressure in the cabin body is 0.01Pa-1 × 106Carrying out constant-pressure regulation or variable-pressure regulation in the Pa range;
preferably, the pressure in the cabin body is between 1000Pa and 5 × 105And carrying out constant-pressure regulation or variable-pressure regulation in the Pa range.
In a particular embodiment of the invention, the pressure in the chamber is set to a certain value, and the controllable gas outlet valve is opened when the pressure rises. When the pressure is reduced, the controllable air inlet valve is opened, and the pressure is continuously fed back to maintain unchanged. The pressure intensity in the cabin body is set to be in a certain speedWhen the pressure in the cabin body is reduced according to a certain speed, the opening of the controllable air inlet valve is adjusted to be realized, the controllable air inlet valve is connected with high-pressure nitrogen, the controllable air outlet valve is connected with a vacuum pump, and the pressure of the cabin body can be realized to be 0.01Pa-1 × 106Constant pressure and variable pressure are adjusted in Pa range, and the pressure is preferably in the range of 1000Pa-5 × 105Pa。
The pressure-adjustable cabin body is a pressure-bearing closed cabin body and can be used under positive pressure and negative pressure. In a specific embodiment of the present invention, the pressure-adjustable cabin further comprises a cabin door, an observation window, a controllable air inlet valve, a pipeline cold trap, a controllable air outlet valve, an electrode flange, a pressure gauge, an exhaust valve, and a safety valve. The electrode flange is used for connecting the heating output of the temperature control device outside the cabin and the thermocouple to the inside of the cabin; the pressure gauge is used for monitoring the pressure in the cabin in real time; the pipeline cold trap is connected with the cabin body and the controllable air outlet valve, so that residual selenium is adsorbed on the pipe wall to avoid influencing the work of the vacuum pump; the controllable air outlet valve is connected with a vacuum pump; the controllable air inlet valve is connected with high-pressure nitrogen, and the high-pressure nitrogen can increase the air pressure in the cabin body through the controllable air inlet valve; the controllable air outlet valve and the vacuum pump are used for reducing the air pressure in the cabin body; the pressure gauge, the controllable air inlet valve and the controllable air outlet valve are all connected with the computer, so that the purpose of continuously controlling the air pressure in the cabin body by a program is achieved, and the air pressure in the cabin body can be adjusted to be high, low and maintained. The change of the air pressure in the cabin body can influence the time and the concentration of the selenium steam reaching the surface of the prefabricated film, and further influence the selenization reaction.
In the specific embodiment of the invention, solid selenium particles or selenium powder are placed in the annular area around the selenium source area of the upper section, the top is sealed, the middle pipeline is connected with the gas treatment area, and the temperature can be set within the range of 200-600 ℃. Selenium steam formed by heating a selenium source arranged in the annular area upwards reaches a certain height and then downwards enters the gas treatment area from the middle pipeline. The gas treatment area in the middle section is a pipeline with a thinner inner diameter, which is beneficial to fully heating gas, and the temperature can be set within the range of 500-. The gas treatment area has higher temperature, and can crack the macromolecular selenium steam evaporated and diffused from the selenium source area into micromolecular selenium steam. The lower selenization reaction area contains air vents which are used for communicating the chamber body with the selenization reaction area in the graphite container, so that the pressure inside and outside the graphite container is consistent, and the lower selenization reaction area can be used for recovering residual selenium. The selenization reaction area is used for placing a prefabricated film to be selenized, and the temperature can be set within the range of 400-. Selenium vapor from the gas processing area reaches the selenization reaction area to perform selenization reaction with the prefabricated film.
In the embodiment of the invention, the inverted selenization device which forces the selenium vapor to diffuse from top to bottom is favorable for controlling the concentration of the selenium vapor.
In a specific embodiment of the present invention, in order to prevent selenium from permeating into the interior of the graphite container, a quartz liner may be installed in the graphite container. The quartz inner container is also divided into a selenium source area, a gas processing area and a selenization reaction area from top to bottom. The graphite container is tightly attached to the quartz inner container, so that a stable temperature field is provided for three regions of the quartz inner container.
In the specific embodiment of the invention, solid selenium particles or selenium powder are placed in the peripheral annular area of the selenium source area of the quartz liner, the top of the quartz liner is sealed, the middle pipeline is connected with the gas treatment area, and the temperature can be set within the range of 200-600 ℃. Selenium steam formed by heating a selenium source arranged in the annular area upwards reaches a certain height and then downwards enters the gas treatment area from the middle pipeline. The gas treatment area in the middle section is a pipeline with a thinner inner diameter, which is beneficial to fully heating gas, and the temperature can be set within the range of 500-. The gas treatment area has higher temperature, and can crack the macromolecular selenium steam evaporated and diffused from the selenium source area into micromolecular selenium steam. The lower selenization reaction area contains air vents which are used for communicating the chamber body with the selenization reaction area in the graphite container, so that the pressure inside and outside the quartz liner is consistent, and the lower selenization reaction area can be used for recovering residual selenium. The selenization reaction area is provided with a prefabricated film to be selenized, the temperature can be set within the range of 400-.
In the specific embodiment of the invention, the computer control system is connected with the temperature control system and can control the heating rates, the temperature maintaining time and the heating interval time of the three temperature regions of the selenium source region, the intermediate gas treatment region and the selenization reaction region. Meanwhile, the computer control system can also control the pressure maintenance, pressurization or depressurization of the chamber pressure. So as to accurately control the time and concentration of the selenium steam reaching the surface of the prefabricated film, thereby obtaining the high-quality copper-zinc-tin-sulfur-selenium crystal.
The invention has the following beneficial effects:
the device and the method can accurately control the time and the concentration of the selenium steam reaching the surface of the prefabricated film, thereby preparing the high-quality copper-zinc-tin-sulfur-selenium crystal.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
fig. 1 is a schematic diagram of a selenization apparatus in accordance with an embodiment of the present invention;
fig. 2 is a schematic view of the combination of a quartz liner and a graphite container according to an embodiment of the present invention.
Reference numerals:
1-a selenization device of copper zinc tin sulfide thin film material; 11-a cabin body; 111-evacuation valve; 112-a safety valve; 113-a controllable inlet valve; 1131-high pressure nitrogen; 114-a pressure gauge; 115-electrode flange; 1151-temperature control system; 116-pipe cold trap; 1161-a controllable gas outlet valve; 1162-vacuum pump; 12-a graphite container; 121-selenium source region; 122-a gas treatment zone; a 123-selenization reaction zone; 124-air guide holes; 125-a selenium source; 126-pre-made film; 127-a thermocouple; 128-a protrusion; 129-quartz inner container; 13-infrared heating jacket; 131-a heating wire; 14-computer control system.
Detailed Description
Referring now to the drawings, an illustrative embodiment of the selenization apparatus for copper zinc tin sulfide thin film materials disclosed in the present invention will be described in detail. Although the drawings are provided to present some embodiments of the invention, the drawings are not necessarily drawn to scale with respect to the specific embodiments. The position of some components in the drawings can be adjusted according to actual requirements on the premise of not influencing the technical effect.
FIG. 1 shows a selenization apparatus 1 for Cu-Zn-Sn-S thin film material of the present invention, which comprisesComprises a cabin body 11, a graphite container 12, an infrared heating jacket 13 and a computer control system 14, wherein the cabin body 11 can bear 0.01Pa-1 × 106A pressure-bearing closed cabin body with pressure of Pa, an electrode flange 115 is arranged on the cabin body, and a graphite container 12 and an infrared heating sleeve 13 are arranged in the cabin body; the graphite container 12 is vertically arranged, and the graphite container 12 comprises a selenium source region 121 positioned at the upper section, a gas treatment region 122 positioned at the middle section and a selenization reaction region 123 positioned at the lower section; the selenium source region 121 and the gas processing region 122 and the selenization reaction region 123 are hermetically connected with each other through threads and gaskets; thermocouples 127 are respectively arranged in the side walls of the upper section, the middle section and the lower section of the graphite container 12; the infrared heating jacket 13 is arranged around the graphite container 12, and the infrared heating jacket 13 includes three sections respectively corresponding to the selenium source region 121, the gas processing region 122 and the selenization reaction region 123; three sections of the infrared heating jacket 13 are respectively provided with a heating wire 131; the electrode flange 115 is used to connect a temperature control system 1151 external to the enclosure 11 to the thermocouples 127 and heater wires 131 within the enclosure 11; the computer control system 14 is coupled to a temperature control system 1151 for controlling the temperature within the enclosure 11.
In this embodiment, the cabin 11 is further provided with a controllable air inlet valve 113, a pressure gauge 114, a pipeline cold trap 116 and a controllable air outlet valve 1161; the controllable air intake valve 113 is connected with high-pressure nitrogen 1131; the pressure gauge 114 is used for monitoring the pressure in the cabin 11 in real time; the pipeline cold trap 116 is used for connecting the cabin 11 and the controllable gas outlet valve 1161; the controllable air outlet valve 1161 is connected with a vacuum pump 1162. The cabin 11 is further provided with an evacuation valve 111 and a safety valve 112.
In this embodiment, the controllable inlet valve 113, the pressure gauge 114 and the controllable outlet valve 1161 are connected to the computer control system 14 to realize real-time control of the pressure in the chamber 11.
In this embodiment, the lower section of the graphite container 12 is provided with a gas guiding hole 124, and the gas guiding hole 124 is used for communicating the chamber body 11 and the selenization reaction zone 123. In the present embodiment, the top of the selenium source region 121 is sealed, and the upper end of the pipe constituting the gas treatment region 122 forms a protrusion 128 communicating with the selenium source region 121 with respect to the bottom of the selenium source region 121.
Fig. 2 is a schematic view of the combination of the quartz liner and the graphite container of the selenization apparatus of the present invention. Referring to fig. 2, the inner wall of the graphite container 12 of the present embodiment is provided with a quartz inner container 129, and the quartz inner container 129 is used for preventing selenium from permeating into the wall of the graphite container 12.
Method of producing a composite material
Example 1
Adding 1.76mmol copper powder, 1.24mmol zinc powder, 1.0mmol tin powder, 588mg dithiodiglycolic acid, 1.0 ml thioglycollic acid, 2 ml 25-28% ammonia water, 1 ml water and 2 ml methanol into a reaction bottle, heating, stirring and dissolving to form a copper-zinc-tin precursor solution, forming a film on a molybdenum glass substrate by a spin coating method, heating and decomposing at 400 ℃, and obtaining a prefabricated film containing copper, zinc, tin and sulfur with the thickness of about 1100nm by changing the times of spin coating/annealing;
placing 10g selenium particles into a selenium source region annular container, placing the prefabricated film to be selenized prepared by the solution method into a selenization reaction region with the front surface of the film facing downwards, adjusting the distance between the prefabricated film and the wall surface of a graphite container to be 1mm, after the placement is finished, integrally placing the prefabricated film into an adjustable ballast, connecting a heating wire and a thermocouple wire, closing a cabin door, pumping air in the cabin body by using a vacuum pump, supplementing high-pressure nitrogen into the cabin body, repeatedly replacing for 3 times, and finally adjusting the pressure of the cabin body to be 1.2 × 10 by a computer control system5Pa and keeping the pressure unchanged. The temperature in the cabin body is controlled by a computer control system. The temperature in the cabin body is controlled by the computer control system according to the following conditions:
setting the heating rate of the selenium source area to be 200 ℃/min, setting the temperature to be 25 ℃ and starting to heat to 565 ℃ for 30 min; setting the heating rate of the gas treatment area to be 300 ℃/min, setting the temperature to be 25 ℃, and starting to heat to be 685 ℃ and maintaining for 30.5 min; setting the heating rate of the selenization reaction zone at 500 ℃/min, setting the temperature to be 25 ℃ and starting to be heated to 525 ℃ and maintaining for 12 min; and after the temperature programming of the selenium source area and the gas processing area is started for 19.7min, the temperature programming of the selenization reaction area is started again.
Preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained CZTSSe light absorption layer film by the selenized copper-zinc-tin-sulfur-selenium film through a chemical water bath method; then sputtering a high-resistance ZnO thin film of 70nm by radio frequency and a transparent conductive ITO thin film of 220nm by direct current, and finally evaporating a Ni-Al metal gate electrode to obtain the CZTSSe thin film solar cell. And testing the photoelectric conversion efficiency of the obtained CZTSSe thin-film solar cell, wherein the efficiency reaches 8%.
Example 2
Adding 1.76mmol copper powder, 1.24mmol zinc powder, 1.0mmol tin powder, 588mg dithiodiglycolic acid, 1.0 ml thioglycollic acid, 2 ml 25-28% ammonia water, 1 ml water and 2 ml methanol into a reaction bottle, heating, stirring and dissolving to form a copper-zinc-tin precursor solution, forming a film on a molybdenum glass substrate by a spin coating method, heating and decomposing at 400 ℃, and obtaining a prefabricated film containing copper, zinc, tin and sulfur with the thickness of about 1100nm by changing the times of spin coating/annealing;
placing 5g of selenium particles into a selenium source region annular container by adopting a graphite container selenizing device with a quartz inner container, placing a prefabricated film to be selenized prepared by the solution method into a selenizing reaction region, integrally placing the selenizing reaction region into an adjustable pressure cabin, connecting a heating wire and a thermocouple wire, closing a cabin door, pumping air in the cabin body by using a vacuum pump, supplementing high-pressure nitrogen into the cabin body, repeatedly replacing for 3 times, finally adjusting the pressure of the cabin body by using a computer control system, controlling the pressure in the cabin body by using the computer control system, namely controlling the pressure in the cabin body according to the following condition that the initial pressure is set to be 2.0 × 105Pa maintenance and timing, after 10min, the chamber pressure is 1.0 × 104The speed of Pa/min is reduced to 1.0 × 105Pa, then maintaining a pressure of 1.0 × 105Pa to the end of the experiment. Simultaneously, the temperature in the cabin body is controlled by the computer control system. The temperature in the cabin body is controlled by the computer control system according to the following conditions: setting the heating rate of the selenium source area to be 200 ℃/min, setting the temperature to be 25 ℃ and starting to heat to 565 ℃ for 20 min; setting the heating rate of the gas treatment area to be 300 ℃/min, setting the temperature to be 25 ℃, and starting to heat to be 685 ℃ and maintaining for 20.5 min; setting the heating rate of the selenization reaction zone at 500 ℃/min, setting the temperature to be 25 ℃ and starting to be heated to 525 ℃ and maintaining for 12 min; when the pressure control starts to time, the temperature programming of the selenium source area and the gas processing area starts, and after 9.7min, the selenylation reaction is carried outThe temperature program begins in the zone.
Preparing a cadmium sulfide buffer layer film with the thickness of about 60nm on the obtained CZTSSe light absorption layer film by the selenized copper-zinc-tin-sulfur-selenium film through a chemical water bath method; then sputtering a high-resistance ZnO thin film of 70nm by radio frequency and a transparent conductive ITO thin film of 220nm by direct current, and finally evaporating a Ni-Al metal gate electrode to obtain the CZTSSe thin film solar cell. And testing the photoelectric conversion efficiency of the obtained CZTSSe thin-film solar cell, wherein the efficiency reaches 11%.
Claims (10)
1. A selenizing device (1) for a copper-zinc-tin-sulfur thin film material comprises a cabin body (11), a graphite container (12), an infrared heating sleeve (13) and a computer control system (14);
the device comprises a cabin body (11), a graphite container (12), an infrared heating sleeve (13), a power supply and a power supply, wherein the cabin body (11) is a pressure-bearing closed cabin body, an electrode flange (115) is arranged on the cabin body, and the graphite container (12) and the infrared heating sleeve (13) are arranged in the cabin body;
the graphite container (12) is vertically arranged, and the graphite container (12) comprises a selenium source area (121) positioned at the upper section, a gas treatment area (122) positioned at the middle section and a selenization reaction area (123) positioned at the lower section; the selenium source region (121) and the gas processing region (122) and the selenization reaction region (123) are hermetically connected with each other; thermocouples (127) are respectively arranged in the side walls of the upper section, the middle section and the lower section of the graphite container (12);
the infrared heating sleeve (13) is arranged around the graphite container (12), and the infrared heating sleeve (13) comprises three sections which respectively correspond to the selenium source area (121), the gas processing area (122) and the selenization reaction area (123); the three sections of the infrared heating jacket (13) are respectively provided with a heating wire (131);
the electrode flange (115) is used for connecting a thermocouple (127) and a heating wire (131) in the cabin (11) to a temperature control system (1151) outside the cabin (11);
the computer control system (14) is connected with the temperature control system (1151) and is used for controlling the temperature of each area in the cabin body (11).
2. The copper zinc tin sulfide thin film material selenization apparatus (1) as claimed in claim 1, wherein the chamber (11) is further provided with a controllable inlet valve (113), a pressure gauge (114), a pipeline cold trap (116) and a controllable outlet valve (1161);
the controllable air inlet valve (113) is connected with high-pressure nitrogen (1131);
the pressure gauge (114) is used for monitoring the pressure in the cabin body (11) in real time;
the pipeline cold trap (116) is used for connecting the cabin body (11) and the controllable gas outlet valve (1161); the controllable air outlet valve (1161) is connected with a vacuum pump (1162).
3. The apparatus (1) for selenizing a zns thin film material of claim 2, wherein the controllable inlet valve (113), the pressure gauge (114) and the controllable outlet valve (1161) are connected to the computer control system (14) to achieve real-time control of the pressure inside the chamber (11).
4. The apparatus (1) for selenizing a copper-zinc-tin-sulfur thin film material according to claim 1, wherein an evacuation valve (111) and a safety valve (112) are further disposed on the chamber body (11).
5. The copper zinc tin sulfide thin film material selenization apparatus (1) as claimed in claim 1, wherein a lower section of the graphite container (12) is provided with a gas guiding hole (124), and the gas guiding hole (124) is used for communicating the chamber body (11) and the selenization reaction zone (123).
6. The apparatus (1) for selenizing a zns thin-film material of claim 1, wherein the top of the se source region (121) is sealed, and the upper ends of the tubes constituting the gas treatment region (122) form a protrusion (128) in communication with the se source region (121) with respect to the bottom of the se source region (121).
7. The copper zinc tin sulfide thin film material selenization device (1) as claimed in claim 1, wherein a quartz liner (129) is disposed on an inner wall of the graphite container (12), and the quartz liner (129) is used for preventing selenium from permeating to the wall of the graphite container (12).
8. The copper zinc tin sulfide thin film material selenization apparatus (1) of claim 1, wherein the sealing connection between the selenium source region 121 and the gas processing region 122 and the sealing connection between the gas processing region 122 and the selenization reaction region 123 are connected through threads and gaskets;
preferably, the cabin (11) can bear 0.01Pa-1 × 106Pressure of Pa.
9. A selenization method of copper zinc tin sulfide thin film material, using the selenization apparatus (1) of any one of claims 1 to 8, comprising the steps of:
placing a selenium source in an annular container of a selenium source area, and simultaneously placing a prefabricated film of a copper-zinc-tin-sulfur thin film material to be selenized in a selenization reaction area; then, connecting a heating wire and a thermocouple wire, and sealing the cabin body; and then, pumping air in the cabin body completely by using a vacuum pump, supplementing high-pressure nitrogen into the cabin body, and finally controlling the temperature and the pressure in the cabin body by using a computer control system, so that selenium steam formed by heating a selenium source is cracked into micromolecular selenium steam through a gas treatment area, then enters a selenization reaction area downwards and performs a selenization reaction with the prefabricated film, and further selenizing the prefabricated film is realized.
10. The method of claim 9, wherein said controlling the temperature within the chamber by the computer control system is controlling the temperature within the chamber by:
the heating rate of the selenium source region is 100 ℃/min-1200 ℃/min, and the temperature is maintained for 10-40min after being heated to 200 ℃ and 1300 ℃;
the temperature rise rate of the gas treatment area is 100-1200 ℃/min, and the temperature is maintained for 10-40min after rising to 200-1300 ℃;
the temperature rise rate of the selenization reaction zone is 100 ℃/min-1200 ℃/min, and the temperature is maintained for 2-40min after being raised to 200 ℃ and 1300 ℃;
preferably, the gas treatment area starts to be heated, and the selenium source area is heated 0-10min after the gas treatment area starts to be heated; and heating the selenization reaction zone 0-20min after the gas treatment zone starts to be heated.
Preferably, the controlling the pressure in the chamber body by the computer control system is to control the pressure in the chamber body according to the following conditions:
the pressure in the cabin body is 0.01Pa-1 × 106Carrying out constant-pressure regulation or variable-pressure regulation in the Pa range;
preferably, the pressure in the cabin body is between 1000Pa and 5 × 105And carrying out constant-pressure regulation or variable-pressure regulation in the Pa range.
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