CN106219502B - A kind of mass production device and mass production method of chalcogenide compound - Google Patents
A kind of mass production device and mass production method of chalcogenide compound Download PDFInfo
- Publication number
- CN106219502B CN106219502B CN201610624614.6A CN201610624614A CN106219502B CN 106219502 B CN106219502 B CN 106219502B CN 201610624614 A CN201610624614 A CN 201610624614A CN 106219502 B CN106219502 B CN 106219502B
- Authority
- CN
- China
- Prior art keywords
- quartz container
- mass production
- chalcogenide
- reaction
- vacuum valve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- -1 chalcogenide compound Chemical class 0.000 title abstract description 21
- 239000010453 quartz Substances 0.000 claims abstract description 127
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 114
- 238000010438 heat treatment Methods 0.000 claims abstract description 63
- 150000004770 chalcogenides Chemical class 0.000 claims abstract description 53
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 25
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- 239000000498 cooling water Substances 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 12
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910052789 astatine Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 239000011669 selenium Substances 0.000 description 37
- 239000010949 copper Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000011135 tin Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000000740 bleeding effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910017000 As2Se3 Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005202 decontamination Methods 0.000 description 3
- 230000003588 decontaminative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- 229910005867 GeSe2 Inorganic materials 0.000 description 2
- 241000233855 Orchidaceae Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 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
- 230000000505 pernicious effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910002059 quaternary alloy Inorganic materials 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 102000010637 Aquaporins Human genes 0.000 description 1
- 108010063290 Aquaporins Proteins 0.000 description 1
- 229910017255 AsSe Inorganic materials 0.000 description 1
- 229910002899 Bi2Te3 Inorganic materials 0.000 description 1
- 108091006146 Channels Proteins 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910005842 GeS2 Inorganic materials 0.000 description 1
- 229910005866 GeSe Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 229910017231 MnTe Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- VTLHPSMQDDEFRU-UHFFFAOYSA-N tellane Chemical compound [TeH2] VTLHPSMQDDEFRU-UHFFFAOYSA-N 0.000 description 1
- 229910000059 tellane Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The present invention provides a kind of mass production method of chalcogenide compound and mass production devices, entire reaction process is divided into main reaction section and back flow reaction section by the present invention, and main reaction section and back flow reaction section are controlled respectively by two independently arranged first heating components and the second heating component respectively, when carrying out main reaction section, first heating component heats reaction to the first part of quartz container, second heating component does not heat, the second part of quartz container keeps lower temperature, so that the high volatile chalcogen simple substance condensation for being evaporated to quartz container second part is deposited on the inner wall of quartz container, to reduce the vapour pressure in quartz container, prevent booster；Then, the second heating component heats the second part of quartz container so that the chalcogen simple substance of deposition is back to quartz container first part and continues to participate in reaction, to maintain the atomic ratio of target chalcogenide.The present invention can be mass chalcogenide, safe and environment-friendly.
Description
Technical field
The present invention relates to the preparation fields of chalcogenide, in particular to a kind of volume production of chalcogenide compound
Method and mass production device.
Background technology
Using the method for vacuum melting come to produce compound be not novel technology.For example, industrial quarters is commonly true
Empty induction melting (Vacuum Induction Melting) exactly utilizes the induction of alternating current to make metallic conductor in a vacuum
Vortex is generated to be heated to metal molten, and fully reaction occurs, is finally crystallized while cooling, and form relevant compound.
The non-volatility memory chip field of a new generation but with many novel technology applications, such as just in exploitation, just needs
Use many chalcogenide compounds, such as GeSe2, GeAsSe, GeAsSeTe, As2Se3Deng.Especially film of new generation
Solar cell is to copper indium gallium selenide (CuInGaSe, CIGS), copper-zinc-tin-sulfur (Cu2ZnSnS4, CZTS) and In2Se3Etc. compounds
Demand it is big, have a vast market.
However, the mass production of these compounds and traditional metallic compound volume production have prodigious difference：(1) it is formed
The higher chalcogen of the element of these compounds, especially volatility can be formed very during heating in reaction cavity
High vapour pressure, the container of reaction allow for bearing very high pressure, therefore the requirement to reaction vessel and technological process
It can be very different with traditional vacuum melting；(2) drain evaporation due to chalcogen in heating reaction process uses
Traditional equipment and technique so that the ratio serious unbalance of the atomic ratio relative ideal in the compound of formation；(3) sulfur family member
Element itself has the function of corrosion to many materials, for example, Se, S etc. and many metal materials can react/corrode, therefore
When selecting the inner-wall material of container or cavity, just limited by many；(4) it participates in the element of reaction and is formed by
It is all insulator or semiconductor that compound is most of, therefore should not be heated using radio frequency induction.
Although the equipment of commercialization volume production compound is substantially vacuum induction melting furnace type on the market at present, can
For producing various metallic compounds, but be not suitable for the chalcogenide compound of production sulfur family.So currently used for producing sulphur
The device of the chalcogenide compound of race is still largely small-scale laboratory home-built equipment, does not form scale metaplasia
The ability of production, it is following method to be usually taken：In the quartz test tube of high-purity, according to the weight ratio of chemical composition
Various elements to be reacted are put into, including the chalcogen of high volatile.The vacuum that the quartz test tube is pumped into, by test tube
Import with acetylene burning things which may cause a fire disaster melt close.This closed quartz ampoule is placed into temperature control heating stove.Temperature-rise period and heating
Temperature need to be determined by the fusing point and reaction property of the compound.These elements are heated to molten condition and are fully reacted.
Since these reactions are all usually exothermic reactions, can in vitro be formed along with the steam for having high volatile gas.Deng fully
After reaction uniformly, the temperature of reacting furnace is gradually decreased to room temperature.Then quartz ampoule is broken, the compound of taking-up is exactly required
The chalcogenide compound wanted.This laboratory prepare on a small scale chalcogenide have the shortcomings that it is as follows：
Excessively high vapour pressure is formed in order to prevent, and the chalcogenide compound amount that can be produced is very small.Depending on stone
The compression strength of English tubular container, in the case where usual quartzy tube thickness is 3~5mm, the chemical combination object amount that maximum can produce is not
More than 500 grams, the vapour pressure size that is primarily limited in entire reaction process.When the amount reacted higher than this numerical value when
It waits, fierce reaction is along with the chalcogen steam released, and quartz container often even explode by rupture.
Contain the elements such as selenium (Se), sulphur (S) or tellurium (Te), the vapour pressure of these elements inside usual chalcogenide
The amount for increasing or processing with the temperature in container increases, and the growth of exponential form is presented in vapour pressure, can be according to Arrhenius
Equation calculation obtains.If the vapour pressure of these elements is revealed because of the breakage of reaction vessel, it is easy to and in ambient atmosphere
Moisture react, be formed with severe toxicity H2Se, H2Te or H2S etc. causes serious safety accident and serious to environment
It threatens.
Also, high volatile chalcogen will appear drain evaporation in reaction process is melted in heating, to make last shape
At compound atomic ratio can not be well controlled, the technical indicator of material is just unable to reach requirement.
In addition, quartz ampoule reaction vessel is merely able to disposable, cause to waste, cost also correspondingly improves.
Therefore, continuous increased market demand and the circumstances of production equipment technological lag are faced, is badly in need of now a kind of
Suitable for the preparation method for producing chalcogenide in batches and corresponding preparation facilities.
Invention content
The purpose of the present invention is to provide a kind of mass production devices of chalcogenide, can produce with high-vapor-pressure
Chalcogenide compound, and it is safe and environment-friendly, and device may be reused, and be produced suitable for automation control.
Another object of the present invention is to provide a kind of mass production methods of chalcogenide, and can mass produce has
The chalcogenide compound of high-vapor-pressure, and it is safe and environment-friendly, and the chalcogenide quality prepared is high.
What the embodiment of the present invention was realized in：
A kind of mass production device of chalcogenide, including quartz container, vacuum valve module and outer cover, quartz container setting
In in outer cover, it is outer and connect with the opening of quartz container that vacuum valve module is set to outer cover, quartz container include first part with
And second part, second part between first part and vacuum valve module, be provided between outer cover and quartz container with
Corresponding first heating component of first part and the second heating component corresponding with second part.
A kind of mass production method of chalcogenide, the mass production method are to prepare chalcogenide using above-mentioned mass production device
, mass production method includes the following steps：
Non- chalcogen simple substance and sulfur family are weighed according to the atomic ratio of each element in the molecular formula for preparing chalcogenide
Element simple substance is as reaction raw materials；
Reaction raw materials are placed in the first part of quartz container and are reacted under vacuum, in the main reaction time
In section, first part is heated by the first heating component, until reaction raw materials are in molten condition, is then carried out at heat preservation
Reason；
In reflux time section, reduces the temperature of first part and the temperature after reducing is made to be not less than sulfur family chemical combination
Then the melting temperature of object heats second part by the second heating component, while heating, vacuum valve module, until point
The deposit not being deposited on second part and vacuum valve module, which melts and is back to first part, continues to participate in reaction；And
Cooling treatment is carried out to quartz container, until reaction product is cooled to solid, obtains chalcogenide.
The advantageous effect of the embodiment of the present invention is：
(1) present invention, which is suitable for fairly large industrial volume production, has the chalcogenide compound of high-vapor-pressure, and shows
It is to be applicable in the sample of small lot production laboratory to have the preparation method of technology.
(2) present invention forms two temperature with temperature gradient by the first heating component and the second heating component and controls
Area can efficiently control the vapour pressure in quartz container.Therefore in fairly large production process, be not in " booster " or
The problems such as leaking of person's pernicious gas can ensure that system safely operates, environment is not affected in process of production.
And existing technology vapour pressure in cavity is formed it is very sensitive, be merely able to by limitation produce very little amount, otherwise just having can
The problem of the safety and environmental protection such as " booster " can occur.
(3) method and apparatus that the present invention prepares chalcogenide, can automatically control production with PLC/GUI to realize,
To reach homogeneity of product and stability, this has apparent advantage than traditional laboratory installation；
(4) equipment container and component of the invention, may be reused.And traditional laboratory installation, quartzy tubular container
It is disposably to use, belongs to consumptive material.
(5) methods and apparatus of the present invention can produce every time sufficient amount (>=1Kg) chalcogenide compound, and
It being capable of being consistent property and stability using the product quality that methods and apparatus of the present invention is produced.
Description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached
Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair
The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this
A little attached drawings obtain other relevant attached drawings.
Fig. 1 is the structural schematic diagram of the mass production device of the chalcogenide of the present invention；
Fig. 2 is the partial sectional view of the mass production device of the chalcogenide of the present invention.
Reference numerals list：
The mass production device 100 of chalcogenide；
Quartz container 110；First part 111；Second part 112；Vacuum valve module 120；Outer cover 130；First heating group
Part 140；Second heating component 150；Pressure gauge 160；Vacuum pump interface 170；First flange 121；Second flange 122；Vacuum valve
Door 123；Nickel alloy washer 124；Cooling-water duct 125；Resistance heater 126；Anticorrosive film layer 127；Bleeding point 131；
Decontamination scrubber 132.
Specific implementation mode
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Below in conjunction with the accompanying drawings, the mass production device 100 of the chalcogenide of the present invention is illustrated.
Referring to Fig. 1, the mass production device 100 of chalcogenide of the invention includes quartz container 110, vacuum valve module 120
With outer cover 130.Quartz container 110 is arranged in outer cover 130, and vacuum valve module 120 is connected to the opening of quartz container 110.
Quartz container 110 is the tubular structure with one end open, opening up, is vertically arranged in outer cover 130.Stone
The opening of English container 110 is located at the opening of outer cover 130, and is connected with vacuum valve module in the opening of quartz container 110
120.Therefore, when being vacuumized to quartz container 110, quartz container 110 and vacuum valve module 120 constitute one it is closed
Vacuum reaction space.The quartz container 110 of the present invention is made of the quartz material of high-purity (99.99%), and fusing point is far high
In the fusing point of chalcogenide compound, and inertia is good, intensity is high, is conducive to the chalcogenide for producing high-purity.Quartz holds
Device 110 is slender type pipe, and for common quartz ampoule, thickness is larger, internal diameter is smaller so that quartz container 110
Tube wall can bear the belt stress of bigger, avoid " booster ".According to a preferred embodiment, the wall of quartz container 110
Thickness is 3mm~8mm.According to a preferred embodiment, the internal diameter of quartz container 110 and the ratio of length are 1：(3~6).
The quartz container 110 of the present invention includes first part 111 and second part 112, wherein first part 111 is held far from quartz
The part of the opening of device 110 in structural schematic diagram shown in Fig. 1, is located at the lower part of quartz container 110.Second part 112 is
Close to the part of the opening of quartz container 110, between first part 111 and vacuum valve module 120, knot shown in Fig. 1
In structure schematic diagram, it is located at the top of quartz container 110.The area of second part 112 and the inner surface of first part 111 ratio is (2
~4)：1.That is, 112 proportion of second part of quartz container 110 is more than 111 accountings of first part of quartz container 110
Example, that is, when carrying out main reaction, therefore the inner surface area higher of the second part 112 as low-temperature space is more conducive to
The steam pressure inside quartz container 110 is reduced in the main reaction period, is further avoided " booster ".
Vacuum valve module 120 includes first flange 121, second flange 122, vacuum valve 123 and nickel alloy washer 124.
First flange 121 is connect with quartz container 110, and the quartz container 110 after connection is fixed to the opening of outer cover 130.The
One flange 121 is attached with quartz container 110 by the way of seamless welding, has been fully ensured that inside quartz container 110
Vacuum environment avoids that toxic gas is overflowed pollution environment due to gas leakage.Referring to Fig. 2, first flange 121 includes setting within it
The cooling-water duct 125 and resistance heater 126 in portion, are respectively used to cool and heat first flange 121.As shown in Fig. 2, more
A cooling-water duct 125 is evenly distributed in the inside of first flange 121, and cooling-water duct 125 is connected to external water pipe.It is multiple
Resistance heater 126 is evenly distributed in the inside of first flange 121, and its setting exists relative to cooling-water duct 125
Closer to the side of 110 outer wall of quartz container, resistance heater 126 is electrically connected with external power supply.
Second flange 122 is provided with vacuum pump interface 170 (such as Fig. 1 institutes for connecting vacuum pump in second flange 122
Show).First flange 121 and second flange 122 are separately positioned on the both sides of vacuum valve 123.First flange 121 and second flange
122 are used for the connection of quartz container 110, vacuum valve 123 and vacuum pump (not shown).
Vacuum valve 123 also includes the cooling-water duct 125 being provided at its inner portion and resistance heater 126.It is multiple cold
But aquaporin 125 and multiple resistance heaters 126 are also evenly provided on the inside of vacuum valve 123, and also respectively with
External water pipe is connected with external power supply, for cooling and heating vacuum valve 123 respectively.Resistance heater 126, which is arranged in, to be leaned on
Nearly 110 side of quartz container.In the present embodiment, the inner wall towards quartz container 110 of vacuum valve 123 is provided with anticorrosive film
Layer 127.Its object is to：(1) metal inner surface of vacuum valve 123 will not with it is directly anti-with corrosive chalcogen steam
It answers, extends the service life of vacuum valve 123；(2) purity for forming compound products in container is improved, shape due to corrosion reaction is avoided
At impurity flow back into the reaction product of first part 111 of quartz container 110.According to a preferred embodiment, anti-corruption
It can be zirconium sesquioxide film layer, chemical vapor deposition (CVD) diamond film layer or titanium nitride membrane to lose film layer 127
Layer.It is worth noting that the anticorrosive film layer 127 shown in Fig. 2 includes but is not limited to installation position shown in figure,
The inner wall of signified vacuum valve 123 of the invention includes but is also not limited to horizontal interior walls shown in figure, present invention meaning
Inner wall of the vacuum valve 123 towards quartz container 110 is all vacuum valves for referring to 110 inside of quartz container and being connected to
123 inner surface.It therefore, can be anti-in capable of being both provided with the inner surface being connected to inside quartz container 110 for vacuum valve 123
Corrosion thin film 127.
The vacuum valve 123 of the present invention is preferably VAT valves (Switzerland's brand).Without doubt, unrequited at other
In embodiment, other kinds of vacuum valve 123 in the prior art can be selected, is not listed one by one herein.Vacuum valve 123 is
VAT valves so that the chalcogen atom of high-vapor-pressure does not have vacuum pipe of the channel permeability to leading portion during reaction
And corresponding vacuum pump, so that the atomic ratio of chalcogenide is maintained, while also avoiding corrosive sulphur
The steam of the formation such as race element Se or S corrodes the vacuum equipment and pipeline of front end.It is this to design also greatly
Reduce the maintenance cost to fore vacuum pipeline and vacuum pump.
Nickel alloy washer 124 is for sealing.In the present embodiment, two nickel alloy washers 124 are separately positioned on the first method
Between orchid 121 and vacuum valve 123 and between second flange 122 and vacuum valve 123.Nickel alloy washer 124 has resistance to height
Warm, erosion-resisting feature will not be reacted with the steam generation of chalcogen.Nickel alloy washer 124 can bear up to 750 DEG C
Temperature, mechanical strength and stability are still fine, and the fusing point (Se that 750 DEG C have been far above many chalcogens：217 DEG C,
S：113 DEG C, Te：449 DEG C), there are enough safety coefficients to meet preparation process.
As shown in Figure 1, vacuum valve module 120 further includes pressure gauge 160, for detecting the pressure inside quartz container 110.
Outer cover 130 is set in 110 outside of quartz container.Outer cover 130 is the body structure with opening.Outer cover 130 is opened
Mouth is arranged at the top of it, and size is sufficient to accommodate quartz container 110.Quartz container 110 is held vertically in opening for outer cover 130
In mouthful, and it is connect with the vacuum valve module 120 being arranged outside outer cover.The present invention the outside of quartz container 110 setting outer cover 130 its
Purpose is, prevents the safety accident that may occur, makes provision against emergencies.For example, just in case in chalcogenide forming process, occur
The fragment of these ruptures and reactant can be blocked, be unlikely to cause safe thing by vessel breaks or demolition accident, outer cover 130
Therefore accidentally injure crowd.Preferably, outer cover 130 is made of stainless steel material.According to a preferred embodiment, outer cover 130 also wraps
Bleeding point 131 is included, decontamination scrubber (Scrubber) 132 is installed outside bleeding point 131.The bleeding point 131 of outer cover 130 is used for
To in outer cover 130, that is, the space between outer cover 130 and quartz container 110 is evacuated, and is allowed to form the building ring of negative pressure
Border.When just in case causing leakage or booster, due to being in negative pressure state in outer cover 130, under the action of atmospheric pressure inside it
Toxic gas does not just overflow, and effectively prevents toxic gas leakage.When the later stage need that the gas inside outer cover 130 is discharged,
Decontamination scrubber 132 mounted on bleeding point 131 can be filtered pernicious gas processing so that the gas of discharge can expire
The pollution emission standard of foot country.
First heating component 140 and the second heating component 150 are arranged between quartz container 110 and outer cover 130, and point
First part and the second part of quartz container 110 are not corresponded to.First heating component 140 controls the main reaction of first part 111
Temperature.Second heating component 150 controls the back flow reaction temperature of second part 112.Added according to a preferred embodiment, first
Hot component 140 and the second heating component 150 are made of refractory brick and resistive heater, and resistive heater is embedded in refractory brick
It is interior, first part 111 and second part 112 are heated by heat radiation.First heating component 140 and the second heating component
150 connect with external temperature control system respectively, to be controlled into trip temperature.
It is worth noting that the mass production device 100 of chalcogenide of the invention can combine with automatic control device
It uses, to realize the automation control to entire chalcogenide preparation process, realizes mass automatic production.According to difference
Chalcogenide prepares required process conditions difference, passes through the pre-set relevant parameter of program.Specifically, non-chalcogen
The fusing point of simple substance, the fusing point of chalcogen simple substance, required reaction temperature, the fusing point of target chalcogenide and corresponding phasor
Deng then according to the corresponding soaking time of the temperature setting of aforementioned list, rate of heat addition etc..Concrete operations, will be in following implementations
Illustrate in example.
In order to make reaction carry out more fully and uniform, when carrying out main reaction period and reflux time section,
The device of the invention is placed on the platform that frequency is 1Hz~2Hz and is shaken, reaction uniformity is improved.
Using above-mentioned mass production device, the mass production method of chalcogenide of the invention includes the following steps：
Step 1：It is on the waiting list raw material
Non- chalcogen simple substance and sulfur family are weighed according to the atomic ratio of each element in the molecular formula for preparing chalcogenide
Element simple substance is as reaction raw materials.
In preferred embodiments of the present invention, above-mentioned non-chalcogen includes Ge, In, Ga, Cu, Zn, Sn, As, Cd and Bi
At least one of, above-mentioned chalcogen is one or both of S, Se and Te.
Preferably, non-chalcogen includes the 1-3 kinds in Ge, In, Ga, Cu, Zn, Sn, As, Cd and Bi.
Step 2：Main reaction
Reaction raw materials are placed in quartz container 110 and are reacted under vacuum.
Within the main reaction period, first part 111 is heated by the first heating component 140, until reaction is former
Material is in molten condition, then carries out isothermal holding.Specifically, it is (2~10) × 10 that vacuum condition, which is, for example, pressure,-4Pa's is true
It is empty.Within the main reaction period, when being heated to the first part 111 of quartz container 110, the liter of the first heating component 140
Warm rate is 5 DEG C/min~12 DEG C/min.Soaking time needed for isothermal holding is 0.5h~3h.
Within the main reaction period, the first part 111 of quartz container 110 is added by the first heating component 140
Heat, reaction raw materials are fused into molten condition, and in this process, reaction is more violent, and supervenes a large amount of heat.To
A part 111 is also required to control second part into trip temperature while heating, but the difference is that, in main reaction
Between in section, second part 112 is not heated, room temperature is maintained.In addition, the temperature of control vacuum valve module 120 room temperature extremely
In the range of 50 DEG C, such as to cooling-water duct 125 it is passed through cooling water, and the resistance heater 126 in first flange 121
No power makes first flange 121 be in relatively low temperature, and general control is in the range of room temperature is to 50 DEG C.In this way, just obtaining
It is in low-temperature space to obtain interior in high-temperature region and second part 112 in first part 111.Since chalcogen belongs to low melting point, Gao Hui
Hair property element, it is easy to form steam, therefore, into quartz container 110 second part 112 chalcogen steam just compared with
It is solidified on the inner wall of the second part 112 of low temperature and the inner wall of first flange 121 and deposits.Since steam is by gaseous state
It is condensed into solid-state, air pressure reduces, and the internal pressure that entire cavity is born also is decreased, avoided " booster " with this so that holds
Key reaction in device carries out within the scope of the container pressure of safety.
Step 3：Back flow reaction
When the main reaction period, fundamental reaction was complete, reflux time section is initially entered.In actual mechanical process,
For main reaction, whether the reaction was complete to be determined according to the reaction time of prepared chalcogenide, it is considered that is warming up to
After undergoing heat preservation 0.5h~3h after required main reaction temperature, main reaction fundamental reaction is complete, can proceed by back flow reaction.
When carrying out back flow reaction, the main reaction of first part still persistently carries out, and only reacts more slowly.It is worth noting that
Signified back flow reaction of the invention is not limited only to chemically react, and the phase transition process of same substance is also signified reaction of the invention.
In reflux time section, second part 112 is heated by the second heating component 150, while passing through electricity
Resistance silk heater 126 heats first flange 121, makes to be deposited on 121 inner wall of 112 inner wall of second part and first flange
On the deposit based on chalcogen simple substance melt and be back to the first part 111 of quartz container 110, continue to participate in anti-
It answers, with the atomic ratio of chalcogenide needed for maintenance.
It should be noted that when carrying out reflux time section, the temperature of first part 111 needs to reduce, but after reduction
Temperature be not less than chalcogenide melting temperature so that the reaction product in first part 111 is still in molten condition.
When carrying out back flow reaction, the temperature of first part 111 is reduced, it is intended that the deposit after fusing is enable all to return
The first part 111 for flowing to quartz container 110 continues to participate in reaction.Because if first part 111 keeps previous reaction temperature
Degree, temperature is excessively high, and molten state deposit can be gasificated into steam again during downward reflux, cannot be introduced into first
Divide and participates in main reaction.Meanwhile the temperature after the reduction of first part 111 is not less than the melting temperature of chalcogenide, purpose again
It is, the main reaction in first part 111 is kept to continue, so that reaction is carried out more abundant.
The second part 112 of quartz container 110 is heated by the second heating component 150, and is existed by setting
Resistance heater 126 in vacuum valve 123 heats vacuum valve 123 so that second part 112 inner wall with
And the chalcogen simple substance of the inner wall deposition of vacuum valve 123 is melted and is flowed back into the reaction zone of main body and continues to participate in reaction,
In this way, the atomic ratio of required chalcogenide is just maintained and is controlled, to obtain high-purity and in strict accordance with mesh
Mark the chalcogenide of atomic ratio.The present invention by the second heating component 150 to the second part 112 of quartz container 110 into
Heating of the resistance heater 126 to vacuum valve 123 in row heating and vacuum valve 123, can make to be deposited on second
Divide the deposit of 123 inner wall of 112 inner walls and vacuum valve, includes mainly sulphur simple substance (S), selenium simple substance (Se) or tellurium simple substance (Te)
Fusing, and it is back to the first part 111 of quartz container 110 and non-chalcogen continues to react, to generate with mesh
Mark atomicity than chalcogenide, and then prepare high-purity chalcogenide, meet technical indicator when application.
Step 4：Cooling step
Cooling treatment is carried out to quartz container 110, until reaction product is cooled to solid, obtains chalcogenide.It is above-mentioned
Cooling treatment is that quartz container 110 is naturally cooled to room temperature.In preferably implementation of the invention, above-mentioned cooling treatment is to utilize
Nitrogen carries out convection current cooling to 110 outer wall of quartz container, to shorten cooling time, improve production efficiency.
Step 5：Aeration step
It may also include aeration step after cooling treatment, so that the inside of quartz container 110 keeps flat with external atmosphere pressure
Weighing apparatus.Preferably, to being passed through nitrogen in quartz container 110.Specially：When all components in quartz container 110 all reach room temperature
When, vacuum valve 123 is opened, nitrogen is slowly led in quartz container 110, until and external pressure balance.Then, the is opened
One flange 121, the compound taken out are exactly high-purity, in strict accordance with the chalcogenide compound of atomic ratio.
With reference to specific embodiment, the mass production method of the mass production device 100 using chalcogenide compound is made into one
Walk explanation.The vacuum valve 123 used due to the preferred embodiment cited by the present invention for VAT valves, in following implementations
VAT valves 123 are vacuum valve 123 in example.
Embodiment 1：CuSe2The preparation of compound
It is 4 kilograms, purity by gross weight>The copper (Cu) and selenium (Se) small spherical particles of=4N is according to atomic ratio Cu:Se=1:
2, or corresponding weight ratio Cu：Se=1：0.4 ratio, that is, copper 1.14Kg, selenium 2.86Kg are put into the quartz container 110
It is interior, first flange 121, second flange 122 and nickel alloy washer 124 are used into screw locking.Start vacuum pump to take out very system
It is empty.When vacuum degree reaches 5x10-4When Pa, VAT valves are shut.Quartz container 110, first flange 121 and VAT valves are constituted
One closed vacuum reaction space.In the present embodiment, the thickness of quartz container 110 is 4mm, the ratio of internal diameter and length
It is 1：3, and the area ratio of the inner surface of the second part 112 and first part 111 of quartz container 110 is 2：1.
Within the main reaction period：It controls the first heating component 140 to heat up with 12 DEG C/min, to quartz container 110
First part 111 heated.In this process, the second heating component 150 is not necessarily to any heating, and first flange
121 and VAT valves should control under the action of cooling water at 50 DEG C or less.At this point, quartz container 110 from top to bottom there is
One temperature gradient from high-temperature region to low-temperature space.Since quartz container 110 of the invention is slender type pipe, and quartzy material
Material is not good heat conductor, and therefore, the first part 111 of quartz container 110 and second part 112 can have larger temperature
Spend gradient, even if first part 111 is in very high state of temperature during the reaction, second part 112 can also keep compared with
Low temperature.
Within the main reaction period, when the first heating component 140 rises to 220 DEG C or so, Se elements melt completely,
Part Se elements generate steam and rise to the second part 112 of quartz container 110.Se atoms after melting can be with solid Cu
Reaction takes place in atom.Since the reaction is typical exothermic reaction, the practical temperature of Cu and Se in quartz container 110
Degree could possibly be higher than the set temperature of control zone, it can make the atomic reaction of this Cu and Se be further exacerbated by.Continue to add first
The temperature of hot component 140 is improved to 950 DEG C.Main reaction region in this when container has been completely in molten condition.It will be anti-
It answers container in 950 DEG C of temperatures 75 minutes or so, and reaction platform is shaken with the frequency of 1Hz.In the main reaction time
In section, Se atoms and Cu atoms sufficiently and uniformly react.
After the main reaction period completes, technique enters reflux time section.By the temperature of the first heating component 140
It is lowered to 530 DEG C or so.But it is required not to be in the compound atomic ratio of the first part 111 of quartz container 110 at this time
Cu:Se=1:2, but the melt of copper-rich.Because thering are many Se atoms to form steam raising during heating to quartz to hold
It is condensed into solid-state at the inner wall of the second part 112 of device 110 and the inner wall of VAT valves.Start the second heating component 150 at this time,
The second part 112 of quartz container 110 is heated, temperature is improved to 220 DEG C.Simultaneously also by first flange 121, VAT
The temperature control in the regions such as valve is increased to 220 DEG C or so.It is all to be condensate in second part 112 under the action of this temperature
Se atoms on inner wall and VAT valve inner walls start to melt and be back in 530 DEG C of melts of container bottom, continue former with copper
Son reaction.In order to allow the Se atoms and Cu atoms fully haptoreaction of reflux, this reaction unit should with the frequency of 1Hz into
Row shakes, and after keeping the temperature 90 minutes, all element reactions fully finish.
The temperature of the second heating component 150 and the first heating component 140 is adjusted to room temperature at this time, while utilizing room temperature
Nitrogen carries out active convective cooling outside quartz ampoule.When whole container is down to room temperature, VAT valves are opened, nitrogen is slowly drawn
Enter reaction vessel until and external pressure balance.The compound for opening taking-up of the flange out of container is high-purity, strictly
According to the chalcogenide compound CuSe of atomic ratio2。
Embodiment 2：As2Se3The preparation of compound
It is that 2Kg purity is by gross weight>The arsenic (As) and selenium (Se) little particle of=4N is according to atomic ratio As:Se=2:3, or
The corresponding weight ratio of person is As:Se=0.63:1 ratio, that is, arsenic 0.77Kg, selenium 1.23Kg are put into the quartz container 110
In, first flange 121, second flange 122 and nickel alloy washer 124 are then used into screw locking.Reaction vessel is evacuated to very
Reciprocal of duty cycle is 3x10-4Then Pa closes VAT valves.Quartz container 110, first flange 121 and VAT valves constitute one
Closed vacuum reaction space.In the present embodiment, the thickness of quartz container 110 is 6mm, and the ratio of internal diameter and length is 1：4,
And the area ratio of the second part 112 of quartz container 110 and the inner surface of first part 111 is 2.5：1.
Technique enters the main reaction period：The first temperature is controlled to heat up with 10 DEG C/min speed, it will be to quartz container 110
First part 111 is heated, and is heated to 600 DEG C, and maintains the temperature 80 minutes.During this period, the second heating component 150
There is no any heating, first flange 121 and VAT valves to be cooled to 50 DEG C or so under the action of cooling water.Allow this platform with
1Hz frequencies are shaken so that the mixing and reaction of As atoms and Se atoms are more uniform.
After the main reaction period completes, process enters reflux time section：By the second heating component 150
(second part 112 of quartz container 110), VAT valves and first flange 121 are warming up to 230 DEG C；And the first heating component
140 should control at 400 DEG C or so according to the binary phase diagraml of As-Se, temperature (in the embodiment for preparing other chalcogenides
In, the control of temperature is determined also according to corresponding phasor).Under the setting of this temperature, the compound of main reaction region still makes
In molten condition, and positioned at the inner wall of second part 112, the inner wall of first flange 121 and the VAT valves of quartz container 110
The Se elements deposited on the inner wall of door begin to melt and be back to the main reaction region of container bottom along tube wall, keep the temperature 80 minutes
Left and right.During this, the entire platform that reacts still is being shaken with the frequency of 1Hz, so that reaction is more uniform.
After reflux time section is completed, all heating power supplies are begun to switch off, into cooling phase.To quartz container
The nitrogen that 110 outer walls blow room temperature is cooled down with convection current, accelerates the cooling cycle.First flange 121 and VAT valves still pass through cooling water
Cooling.The step can be controlled by program.When reaching room temperature, VAT valves are opened, slow introduction of nitrogen makes quartz container
The pressure and external pressure of 110 inner walls balance.Flange is opened, the compound of taking-up is exactly high-purity, maintains atomic ratio
Binary chalcogenide compound As2Se3。
Embodiment 3：Copper-zinc-tin-sulfur CZTS (Cu2ZnSnS4) quaternary compound preparation
Surface solar cell material of the quaternary alloy copper-zinc-tin-sulfur (CZTS) as a new generation, starts to cause photovoltaic circle
Attention, especially its raw material rich reserves, and this very low notable advantage of cost on earth.But its disadvantage
It is when forming the quaternary compound, the reaction occurred is very fierce, and due to containing high volatile sulphur, because
This is difficult the atomic ratio controlled between its each element.The molecular formula of copper-zinc-tin-sulfur for film photovoltaic material is usually：
Cu2ZnSnS4, ideal atomic ratio is：Cu:Zn:Sn:S=2:1:1:4, corresponding weight percent is：Cu
29.04%, Zn 14.53%, Sn 27.13%, S 29.30%.It is 2Kg, copper of the purity higher than 4N, zinc, tin, sulphur member by gross weight
Plain bead, according to weight：Copper 0.58Kg, zinc 0.29Kg, tin 0.54Kg, sulphur 0.59Kg are put into reaction vessel, then with the first method
Orchid 121 and nickel alloy washer 124 and second flange 122 use screw locking.Vacuum tank is pumped into 5x10-4Pa.In this implementation
In example, the thickness of quartz container 110 is 7mm, and the ratio of internal diameter and length is 1:5, and the second part of quartz container 110
112 and first part 111 inner surface area ratio be 3:1.
Technique enters the main reaction period：Start the heating of main reaction region at once, heating speed should control on the left sides 5 DEG C/min
It is right.The not any heating in first temperature controlled region (second part 112 of quartz ampoule), first flange 121 and VAT valves pass through cooling
Water management is in 40 DEG C or so of low temperature.When main reaction region reaches 235 DEG C, S elements have been in molten condition, start and Zn and Sn
It reacts, and along with having in S steam raisings to the inner wall and VAT valves 123 of the second part 112 of quartz container 110
It is deposited on wall.90 minutes are kept the temperature at 235 DEG C, allows S, Zn and Sn fully to react, and the interfacial reaction with the surfaces Cu.Due to this
It is all exothermic reaction to react a bit, therefore the temperature in quartz container 110, is likely to be greater than the temperature of setting.After 90 minutes,
In the main reaction period, continues to heat up container with 8 DEG C/min speed, its temperature is made to have reached 850 DEG C.It keeps the temperature at this temperature
90 minutes.At this point, each element of all first parts 111 in quartz container 110, fundamental reaction are complete.
Subsequently into reflux time section：650 DEG C will be transferred at a temperature of the first heating component 140 first, then will
The temperature of second heating component 150, first flange 121 and VAT valves is improved to 120 DEG C.It is deposited on quartz container 110 at this time
112 inner wall of second part, the sulphur on 123 inner wall of VAT valves will flow back into 110 first part 111 of quartz container master it is anti-
It answers in area, continues to participate in the reaction of CZTS.The total time of reflux time section controls at 120 minutes or so, so that reaction is had and fills
The dynamics time divided.
In the two above stages, reaction platform is being shaken with the frequency of 1Hz, to promote the uniform mixed of these elements
It closes.
After completing the flow of main reaction period and reflux time section, all heating power supplies are cut off, are allowed
System cools down, into cooling phase.In order to make quartz container 110 quickly cool down, the nitrogen of room temperature can be blown quartz outer tube wall,
It is cooled down with convection type.Flange and VAT valves etc. can be passed through cooling water and be cooled to room temperature.After system reaches room temperature, VAT is opened
Nitrogen is slowly introduced the cavity of quartz container 110 by valve, until reaching balance with external atmospheric pressure.Flange is opened, is taken out
Be exactly it is high-purity, have the CZTS semiconductor quaternary alloys of stringent atomic ratio.
It is worth noting that chalcogenide prepared by the present invention includes but are not limited to mentioned in above-described embodiment
, chalcogenide of the invention further includes following：Cu(In,Ga)Se50、In2Se3、In2S3、AsSe、As4Se3、Cu2Se、
CuSe2、CuSe、Cu2S、CuS、CuSe2、CuInSe2、CuInS2、CuAlS2、CuAlSe2、CuFeS2、Cu2SnSe3、Cu2SnS3、
Cu2ZnSnS4、GeAsSe、GeSe、GeSe2、GeS、GeS2、GeAsSeTe、CdS、CdSe、ZnS、ZnTe、MnTe、SnS、
Bi2Se3、Bi2Te3、Bi2S3, etc..The preparation process of these chalcogenides is roughly the same with above-described embodiment, main difference
It is, reaction temperature, soaking time and heating rate etc. slightly adjust, this is the fusing point and different sulfur families by different elements
What the characteristic of compound was determined.Therefore, it in preparation process, is adaptively adjusted, is not just repeating herein.
Aforementioned cited chalcogenide is still without all chalcogenides of limit.To sum up, the sulphur of the present invention
The mass production method and device of compounds of group are suitable for can be in the preparation of the compound of reaction process formation high-vapor-pressure.Certainly,
The present invention is also not limited to chalcogenide, and mass production method of the invention and device can equally be used to other with low
The preparation of the compound of fusing point, high-vapor-pressure.
Therefore, for those skilled in the art, the invention may be variously modified and varied.It is all the present invention
Within spirit and principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of mass production device of chalcogenide, which is characterized in that the mass production device includes quartz container, vacuum valve module
And outer cover, the quartz container are set in the outer cover, the vacuum valve module be set to the outer cover it is outer and with it is described
The opening of quartz container connects, and the quartz container includes first part and second part, the first part and described the
Two parts be an entirety and be interconnected, the second part between the first part and the vacuum valve module,
Be provided between the outer cover and the quartz container the first heating component corresponding with the first part and with it is described
Corresponding second heating component of second part.
2. the mass production device of chalcogenide according to claim 1, which is characterized in that the quartz container has for one end
There is a tubular structure of the opening, the thickness of the quartz container is 3mm~8mm, the internal diameter of the quartz container and length
Ratio is 1：The area ratio of (3~6), the second part and the inner surface of the first part is (2~4)：1.
3. the mass production device of chalcogenide according to claim 1, which is characterized in that the vacuum valve module includes true
Empty valve, the first flange being connect with the quartz container, the second flange for connecting vacuum pump and nickel alloy washer, institute
It states first flange and the second flange is arranged in the both sides of the vacuum valve, the nickel alloy washer is separately positioned on described
Between first flange and the vacuum valve and between the second flange and the vacuum valve.
4. the mass production device of chalcogenide according to claim 3, which is characterized in that the first flange and described true
Empty valve includes the cooling-water duct and resistance heater being provided at its inner portion.
5. the mass production device of chalcogenide according to claim 3, which is characterized in that the vacuum valve towards institute
It states the inner wall inside quartz container and is provided with anticorrosive film layer.
6. a kind of mass production device using as described in any one of claim 1 to 5 prepares the mass production method of chalcogenide,
It is characterized in that, the mass production method includes the following steps：
Non- chalcogen simple substance and sulfur family are weighed according to the atomic ratio of each element in the molecular formula for preparing the chalcogenide
Element simple substance is as reaction raw materials；
The reaction raw materials are placed in the first part of the quartz container and are reacted under vacuum, in master
In reaction time section, the first part is heated by first heating component, until the reaction raw materials are in molten
Melt state, then carries out isothermal holding；
In reflux time section, reduces the temperature of the first part and the temperature after reducing is made to be not less than the sulfur family
Then the melting temperature of compound heats the second part by second heating component, while described in heating
Vacuum valve module, until the deposit being respectively deposited on the second part and the vacuum valve module is melted and is back to
The first part continues to participate in reaction；And
Cooling treatment is carried out to the quartz container, until reaction product is cooled to solid, obtains the chalcogenide.
7. mass production method according to claim 6, which is characterized in that the non-chalcogen include Ge, In, Ga, Cu,
At least one of Zn, Sn, As, Cd and Bi, the chalcogen are one or both of S, Se and Te.
8. mass production method according to claim 6, which is characterized in that within the main reaction period, control described true
The temperature of empty valve module is in the range of room temperature is to 50 DEG C.
9. mass production method according to claim 6, which is characterized in that within the main reaction period, described first adds
The heating rate that hot component heats the first part is 5 DEG C/min~12 DEG C/min, when heat preservation needed for the isothermal holding
Between be 0.5h~3h.
10. mass production method according to claim 6, which is characterized in that anti-in the main reaction period and the reflux
It answers in the period, the quartz container is shaken on the platform that frequency is 1Hz~2Hz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610624614.6A CN106219502B (en) | 2016-08-02 | 2016-08-02 | A kind of mass production device and mass production method of chalcogenide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610624614.6A CN106219502B (en) | 2016-08-02 | 2016-08-02 | A kind of mass production device and mass production method of chalcogenide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106219502A CN106219502A (en) | 2016-12-14 |
| CN106219502B true CN106219502B (en) | 2018-08-07 |
Family
ID=57535562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610624614.6A Active CN106219502B (en) | 2016-08-02 | 2016-08-02 | A kind of mass production device and mass production method of chalcogenide compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106219502B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10319588B2 (en) * | 2017-10-10 | 2019-06-11 | Asm Ip Holding B.V. | Method for depositing a metal chalcogenide on a substrate by cyclical deposition |
| CN108069462B (en) * | 2018-01-08 | 2019-11-22 | 湖南锐林新能源科技有限公司 | A kind of one-step method batch synthesizes the device and method of high-purity cobalt disulfide |
| CN109270226B (en) * | 2018-11-29 | 2024-04-19 | 江苏省环境科学研究院 | Organic liquid volatilizing and treating device with controllable conditions |
| CN115786751B (en) * | 2022-11-15 | 2024-01-19 | 重庆天齐锂业有限责任公司 | Smelting method of lithium-magnesium-silicon alloy |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2070195U (en) * | 1990-07-19 | 1991-01-30 | 湖南省洪江市三化工厂 | Cracking reactor for soap elements |
| TWI382095B (en) * | 2009-03-04 | 2013-01-11 | Jun Wen Chung | Method for manufacturing multi-element metal chalcogenide synthesis |
| CN104014284B (en) * | 2014-06-04 | 2016-07-06 | 四川大学 | The free fall high-temperature nuclei method of IIB-VIA compounds of group powder and synthesizer |
| CN204699671U (en) * | 2015-06-11 | 2015-10-14 | 济宁学院 | Chemical laboratory reactor |
-
2016
- 2016-08-02 CN CN201610624614.6A patent/CN106219502B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106219502A (en) | 2016-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106219502B (en) | A kind of mass production device and mass production method of chalcogenide compound | |
| JP5075122B2 (en) | Cold wall container method for compounding, homogenizing and compacting semiconductor compounds | |
| CN100464149C (en) | Thermal field structure of polysilicon ingot furnace | |
| US8323408B2 (en) | Methods and apparatus to provide group VIA materials to reactors for group IBIIIAVIA film formation | |
| CN111809242B (en) | Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material | |
| CN101307397A (en) | Vacuum smelting method and apparatus for copper-indium-gallium-selenium photovoltaic material | |
| CN104131339A (en) | Preparation method of polysilicon chip | |
| CN102899720B (en) | Ingot casting method for efficient polycrystalline silicon | |
| CN101311113B (en) | Preparation device and preparation method of high purity polysilicon | |
| US8765036B2 (en) | Method of producing a semiconductor | |
| CN103400895B (en) | A kind of preparation method of copper-zinc-tin-sulfur solar battery obsorbing layer film | |
| CN101688290A (en) | Vacuum evaporation apparatus for solid materials | |
| CN112680781B (en) | Cadmium telluride crystal growth device and growth method thereof | |
| CN104014284B (en) | The free fall high-temperature nuclei method of IIB-VIA compounds of group powder and synthesizer | |
| US20190136345A1 (en) | Device for preparing multi-element alloy compound | |
| US20150020896A1 (en) | Method and device for refilling an evaporator chamber | |
| CN103236472B (en) | The preparation method of CIGS thin film solar cell selenides | |
| CN104178809A (en) | Method for preparing low metal boron master alloy by use of metallurgy method | |
| CN110528081A (en) | A kind of LiXSe2The synthetic method of polycrystalline compounds and monocrystal | |
| JP2007201348A (en) | Purge cell | |
| EP3572560A1 (en) | Single crystal manufacturing device and single crystal manufacturing method | |
| US20170233887A1 (en) | Methods of Producing a Semiconductor with Decreased Oxygen Contamination and Impurities | |
| CN111809241B (en) | Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material | |
| CN111809243B (en) | Method for preparing cadmium telluride or cadmium zinc telluride polycrystal material | |
| US4545848A (en) | HCT Crystal growth method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200529 Address after: West Zone, hi tech Industrial Development Zone, Chengdu hi tech Zone, Sichuan Province Patentee after: Pioneer Materials Inc. Chengdu Address before: Courtyard of San Jose, California 5218 Co-patentee before: Qiu Li'an Patentee before: Li Zongyu |
|
| TR01 | Transfer of patent right | ||
| CP03 | Change of name, title or address |
Address after: Building 1, 2nd Floor, China (Nanjing) Software Valley Xinchuang Industrial Park, No. 6 Mingyuan Road, Yuhuatai District, Nanjing City, Jiangsu Province, 210000 Patentee after: Nanjing Xianfeng Material Technology Co.,Ltd. Country or region after: China Address before: 610000 West District of hi tech Industrial Development Zone, Chengdu hi tech Industrial Development Zone, Sichuan Province Patentee before: Pioneer Materials Inc. Chengdu Country or region before: China |
|
| CP03 | Change of name, title or address |