CN107779844A - Forming method, former and its application method of calcium titanium ore bed film and application - Google Patents
Forming method, former and its application method of calcium titanium ore bed film and application Download PDFInfo
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- CN107779844A CN107779844A CN201610721611.4A CN201610721611A CN107779844A CN 107779844 A CN107779844 A CN 107779844A CN 201610721611 A CN201610721611 A CN 201610721611A CN 107779844 A CN107779844 A CN 107779844A
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- 238000000034 method Methods 0.000 title claims abstract description 59
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 219
- 238000000137 annealing Methods 0.000 claims abstract description 47
- 230000008021 deposition Effects 0.000 claims abstract description 44
- 238000013459 approach Methods 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000010408 film Substances 0.000 claims description 82
- 239000002904 solvent Substances 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 54
- 239000010409 thin film Substances 0.000 claims description 39
- 239000000376 reactant Substances 0.000 claims description 26
- 238000001704 evaporation Methods 0.000 claims description 22
- 230000008020 evaporation Effects 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 230000005669 field effect Effects 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001408 amides Chemical group 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910052789 astatine Inorganic materials 0.000 claims description 3
- RYXHOMYVWAEKHL-UHFFFAOYSA-N astatine atom Chemical compound [At] RYXHOMYVWAEKHL-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 230000003466 anti-cipated effect Effects 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052753 mercury Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052699 polonium Inorganic materials 0.000 claims description 2
- HZEBHPIOVYHPMT-UHFFFAOYSA-N polonium atom Chemical compound [Po] HZEBHPIOVYHPMT-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052716 thallium Inorganic materials 0.000 claims description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 33
- 239000007789 gas Substances 0.000 description 27
- 230000000740 bleeding effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- OQLZINXFSUDMHM-UHFFFAOYSA-N Acetamidine Chemical compound CC(N)=N OQLZINXFSUDMHM-UHFFFAOYSA-N 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000469 dry deposition Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The present invention relates to a kind of forming method of calcium titanium ore bed film,Former and its application method and application,Utilize a tubular housing,Tubular housing is disposed with substrate approach section,Deposit cavity,Adapter cavity,Anneal chamber and substrate take out five parts such as section,Conveyer is set in tubular housing,Objective table is respectively arranged with deposit cavity and anneal chamber,Barometric control unit and heater,Dividing plate is utilized respectively between adjacent segment and chamber and each chamber to separate,The substrate of film to be deposited is placed on frame substrate,By conveyer since substrate approach section,Successively continually by deposit cavity,After adapter cavity and anneal chamber,Finally taken out from substrate and take out the substrate for having deposited calcium titanium ore bed film on the frame substrate of section,Deposition film forming and annealing process are combined together,Realize the consecutive production of calcium titanium ore bed film product.Using the calcium titanium ore bed film crystal even particle size of the device fabrication of the present invention, densification, there is good photoelectric transformation efficiency.
Description
Technical field
The invention belongs to the technical field of calcium titanium ore bed film, more particularly to a kind of forming method of calcium titanium ore bed film,
Former and its application method and application.
Background technology
Solar cell is a kind of electrooptical device, is converted solar energy into electrical energy using the photovoltaic effect of semiconductor.
It is developed so far, solar power generation has become the most important regenerative resource in addition to hydroelectric generation and wind-power electricity generation.It is current in
Commercialized semiconductor has monocrystalline silicon, polysilicon, non-crystalline silicon, cadmium telluride, CIGS etc., but energy consumption is big mostly, cost is high.
In recent years, a kind of perovskite solar cell receives significant attention, and this perovskite solar cell is with organic gold
Category halide is light absorbing layer.Perovskite is ABX3The cuboctahedron structure of type, as shown in Figure 1.Such a material is prepared thin
Film solar cell simple process, production cost are low, stable and high conversion rate, from 2009 so far, photoelectric transformation efficiency from
3.8% is promoted to more than 22%, higher than commercialized crystal silicon solar batteries and has had larger cost advantage.
Various perovskite solar battery thin film moulding process can be divided into two major classes：Solwution method and vapor phase method.Solwution method is grasped
Make simplicity, film forming can be prepared at normal temperatures and pressures, but the thin homogeneity of the perovskite formed is poor, in film microstructure Hole
Too much, leakage current is big, has a strong impact on the efficiency of solar cell, and poor repeatability.Therefore this method is not suitable for extensive, large scale
Production.Vapor phase method has double source coevaporation method, gas phase assisted solution method, chemical vapor deposition（CVD）The methods of.Such as with CH3NH3I and
PbCl2As two evaporation sources, perovskite thin film can be prepared.This method is compared with solwution method, and the film being prepared is more
It is homogeneous.But this method needs high vacuum and higher temperature conditionss, improve cost and can not mass produce.Thus propose gas
Phase assisted solution method solves this problem, and the calcium titanium that crystallite dimension is bigger, covering is more complete, surface roughness is smaller has been made
Ore deposit film.
Low-pressure chemical vapor deposition（LPCVD）The methods of be also applied to prepare perovskite thin film, obtained better performances
Film.Existing Low Pressure Chemical Vapor Deposition（LPCVD）Need to aid in gas, the nitrogenous organic salt of evaporation in deposition process
Halide（AX）Deposit uneven in course of reaction, the putting position of substrate can largely influence property of thin film so that same
There is difference in property of thin film prepared by one batch；Simultaneously, it is impossible to annealed or solvent auxiliary annealing technique after film forming, nothing
Method realizes consecutive production.
The content of the invention
The technical problems to be solved by the invention are, there is provided a kind of forming method, the former of calcium titanium ore bed film
And its application method and application, the reactant homogeneous film formation of making calcium titanium ore bed film under conditions of it need not aid in gas,
And be combined together gas phase-solid phase film forming and annealing process, realize the continuity automated production of calcium titanium ore bed film product.
The present invention, which is achieved in that, provides a kind of forming method of calcium titanium ore bed film, using a tubular housing, in institute
State and substrate approach section is respectively arranged with before and after tubular housing and substrate takes out section, if the tubular housing is respectively arranged with dry deposition
Chamber and/or adapter cavity and/or anneal chamber, objective table, barometric control unit are respectively arranged with the deposit cavity and anneal chamber
And heater, the heater heat to the reactant in objective table, its gas after the reactant heating evaporation
Particle deposit to positioned on substrate surface in the chamber, be utilized respectively dividing plate between adjacent segment and chamber and each chamber
Separate；
The forming method comprises the following steps：The substrate of film to be deposited is placed on frame substrate, by being arranged on tubular cavity
Internal conveyer since substrate approach section, successively continually by some deposit cavities, adapter cavity and anneal chamber after, finally
Taken out from substrate and the substrate for having deposited calcium titanium ore bed film is taken out on the frame substrate of section.
The invention also discloses former made of a kind of forming method principle using above-mentioned calcium titanium ore bed film,
Including tubular housing and conveyer, the conveyer is arranged in tubular housing, is set respectively before and after the tubular housing
It is equipped with substrate approach section and substrate takes out section, the tubular housing is respectively arranged with some deposit cavities and/or adapter cavity and/or moved back
Fiery chamber, the objective table for placing deposition reactant is provided with the deposit cavity, placement annealing is provided with the anneal chamber
The objective table of secondary solvent, it is also respectively provided with the deposit cavity and anneal chamber and places barometric control unit and heating dress
Put, the heater heats to the deposition reactant in objective table and annealing secondary solvent respectively, the deposition reaction
After thing and annealing secondary solvent heating evaporation its gas particles deposit to positioned at film to be deposited in the chamber substrate table
On face, between adjacent segment and chamber and each chamber being utilized respectively dividing plate separates；The substrate of film to be deposited is placed on substrate
On frame, by conveyer since substrate approach section, successively continually by some deposit cavities and/or adapter cavity and/or annealing
After chamber, the substrate for being taken out on the frame substrate of section and having deposited calcium titanium ore bed film is finally taken out from substrate.
Further, the conveyer includes conveyer belt, and the frame substrate is set on a moving belt；The conveyer belt is set
Put in the surface of objective table, the face objective table down to be deposited of the substrate.
Further, the groove for placing substrate is provided with the middle part of the frame substrate, is provided with the middle part of the groove
Recess hole, the groove are slightly larger than substrate, and the recess hole is slightly less than the surface to be deposited of substrate, on the both sides of the frame substrate
It is used for the position for fixing substrate equipped with transversely movable movable substrate fixed plate, the substrate fixed plate is fixed on substrate
The back side.
Further, the objective table top is provided with split-flow baffles, multiple points is provided with the split-flow baffles
Discharge orifice, the reactant gas of the objective table evaporation reach substrate surface again after split-flow baffles.
Further, the heater includes the upper heating plate positioned at deposit cavity and lower heating plate, and positioned at annealing
The upper heating plate of chamber and lower heating plate, the upper heating plate of the upper heating plate and anneal chamber of the deposit cavity is respectively on frame substrate
Substrate heats, and the lower heating plate of the lower heating plate and anneal chamber of the deposit cavity is respectively to the deposition in the objective table of place chamber
Reactant and annealing secondary solvent are heated；The temperature control of the upper heating plate of the upper heating plate and anneal chamber of the deposit cavity
At 30 DEG C ~ 150 DEG C, the objective table temperature control of the deposit cavity is at 100 DEG C ~ 200 DEG C, the temperature of the objective table of the anneal chamber
Control is at 30 DEG C ~ 200 DEG C.
Further, precursor BX is anticipated on the substrate surface of the film to be deposited2, the deposit cavity loading
Deposition reactant in platform is AX, and the molecular structure for the calcium titanium ore bed film that the substrate deposition obtains is ABX3, wherein A is amine
At least one of base, amidino groups or alkali family, B be lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony,
The cation of at least one of osmium, iridium, platinum, gold, mercury, thallium, bismuth, polonium, X are the anion of at least one of iodine, bromine, chlorine, astatine；
Annealing secondary solvent in the anneal chamber objective table is amide solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogen
For any one in varsol, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon solvent；The reaction of the deposit cavity
Time control is controlled in 5min ~ 2h in 5min ~ 2h, the reaction time of the anneal chamber.
The invention also discloses a kind of application method of the former of calcium titanium ore bed film as the aforementioned, the application method
Comprise the steps of：
First step, prepare deposition surface and contain precursor BX2Substrate；
Second step, deposition there is into precursor BX2Some substrates be positioned on frame substrate, open deposit cavity enter dividing plate, will
Frame substrate with substrate is sent in deposit cavity by conveyer through substrate approach section and carries out film forming, treats that frame substrate enters
That deposit cavity is closed after deposit cavity enters dividing plate；Next batch substrate to be deposited is positioned in another frame substrate, is sent to
Subsequent cycle is waited in substrate approach section；
Third step, AX is placed on deposit cavity objective table, the gas pressure in deposit cavity, gas are controlled by barometric control unit
Body pressure limit is 10-5Pa~105Pa；Control the temperature and time of the heater of deposit cavity so that be positioned on objective table
AX, which is heated, is evaporated to gas, the precursor BX in AX gas particles and substrate2React, generate ABX3Type perovskite thin film；
Four steps, the discharge dividing plate of deposit cavity is opened, the substrate that preceding deposition has perovskite is sent to adapter cavity, it is heavy to close
The discharge dividing plate of product chamber；That opens deposit cavity enters dividing plate, and another communicated device of substrate to be deposited is sent into deposit cavity,
Third step is carried out again, starts another deposition working cycles；
5th step, that opens anneal chamber enters dividing plate, and the substrate of film forming is sent in anneal chamber using transmitting device；
Annealing solvent is added on the objective table of anneal chamber；Aforementioned separator plate is closed after frame substrate entrance；
6th step, the pressure of anneal chamber is controlled 10 by barometric control unit-5Pa~105A certain value between Pa；Anneal chamber
Heater a certain value of the temperature between 30 DEG C ~ 200 DEG C；The annealing solvent being positioned on objective table is heated and is evaporated to
Gas, the gas particles for solvent of annealing aid in the ABX on substrate3The further reactive crystallization of type perovskite thin film, complete at annealing
Reason；
7th step, opens the discharge dividing plate of anneal chamber, and frame substrate is sent to substrate by conveyer and takes out section, having deposited calcium
The substrate of titanium ore layer film takes out preservation from frame substrate, completes the working cycles.
Further, the pressure control in the deposit cavity and anneal chamber is 10-5Pa ~105 Between Pa；The deposit cavity
Objective table temperature control at 100 DEG C ~ 200 DEG C；The temperature control of heating plate is at 30 DEG C ~ 150 DEG C on the deposit cavity；It is described
The reaction time of deposit cavity is controlled in 5 min ~ 2h, preferably 10min ~ 60min；The temperature control of the objective table of the anneal chamber
At 30 DEG C ~ 120 DEG C；Temperature of heating plate control is at 30 DEG C ~ 200 DEG C in the anneal chamber；The anneal chamber annealing time control exists
5min~2h。
The invention also discloses a kind of application of the application method of the former of foregoing calcium titanium ore bed film, and being should
For making in solar cell or LED or thin film field-effect pipe.
Compared with prior art, forming method, former and its application method of calcium titanium ore bed film of the invention and
Using using a tubular housing, tubular housing is disposed with substrate approach section, deposit cavity, adapter cavity, anneal chamber and substrate
Five parts such as section are taken out, conveyer is set in tubular housing, objective table, gas are respectively arranged with deposit cavity and anneal chamber
Adjusting means and heater are pressed, being utilized respectively dividing plate between adjacent segment and chamber and each chamber separates, will be to be deposited thin
The substrate of film is placed on frame substrate, by conveyer since substrate approach section, successively continually by deposit cavity, adapter cavity
After anneal chamber, the substrate for being taken out on the frame substrate of section and having deposited calcium titanium ore bed film is finally taken out from substrate, will be deposited into
Film and annealing process are combined together, and are realized the continuity automated production of calcium titanium ore bed film product, are greatly enhanced production
Efficiency.
Brief description of the drawings
Fig. 1 is calcium titanium ore bed thin-film material ABX3Crystal structure schematic diagram；
Fig. 2 is the floor map of a preferred embodiment of the present invention；
Fig. 3 is the top view of split-flow baffles in Fig. 2；
Fig. 4 is the top view of frame substrate in Fig. 2；
Fig. 5 is the top view for the conveyer for being placed with substrate and frame substrate；
Fig. 6 is a kind of manufacture of solar cells process schematic using ITO or FTO as substrate；
Fig. 7 is to be intended to using the battery structure diagram of perovskite solar cell made from the equipment of the present invention；
Fig. 8 is the SEM figures using perovskite thin film made from the equipment of the present invention；
Fig. 9 is the XRD of Fig. 8 perovskite thin film；
Figure 10 is the Current density-voltage of the perovskite solar cell prepared using the equipment of the present invention（J-V）Curve map.
Embodiment
In order that technical problems, technical solutions and advantages to be solved are more clearly understood, tie below
Drawings and Examples are closed, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
It refer to shown in Fig. 2, a kind of forming method of calcium titanium ore bed film disclosed by the invention, be to utilize a tubular housing
2, substrate approach section M1 is respectively arranged with before and after the tubular housing 2 and substrate takes out section M5.In the present invention, substrate enters
It is to be separately positioned in tubular housing 2 and be located at the rear and front end portion of tubular housing 2 that section M1 and substrate, which take out section M5, in situation about having
Under, substrate approach section M1 and substrate take out section M5 and can also be separately positioned on outside tubular housing 2 near its rear and front end portion.
Some deposit cavity M2 and/or adapter cavity M3 and/or anneal chamber M4 are respectively arranged with the tubular housing 2.
In the present invention, a deposit cavity M2, an adapter cavity M3 and an anneal chamber M4 are disposed with respectively in tubular housing 2,
It can required in some cases according to the number of plies of substrate deposition film, multiple deposit cavity M2 be set respectively in tubular housing 2
And/or adapter cavity M3 and/or anneal chamber M4.
The objective table 7 for placing deposition reactant is provided with the deposit cavity M2, is provided with the anneal chamber M4
The objective table 19 of annealing secondary solvent is placed, barometric control unit is also respectively provided with the deposit cavity M2 and anneal chamber M4
1 and 18 and heater 8 and 16.The heater is aided in the deposition reactant in objective table 7 and 19 and annealing respectively
Solvent is heated, after deposition reactant heating evaporation its gas particles deposit to positioned at film to be deposited in the chamber
Reaction forms ABX on substrate surface3Type perovskite.Auxiliary-solvent evaporation particle of annealing aids in perovskite crystal further growth.
Dividing plate 4,12,15 and 20 is utilized respectively between adjacent segment and chamber and each chamber to separate.
The forming method comprises the following steps：
The substrate 9 of film to be deposited is placed on frame substrate 24, by be arranged in tubular housing 2 conveyer 3,10,11,
14 and 22 since substrate approach section M1, successively continually by deposit cavity M2, adapter cavity M3 and anneal chamber M4 after, finally from base
Piece takes out and takes out the substrate 9 for having deposited calcium titanium ore bed film on section M5 frame substrate 24.The deposit cavity M2 is used in substrate 9
Surface deposition calcium titanium ore bed film layer, the adapter cavity M3 is used to transmit and of short duration deposition of placing has the substrate of perovskite thin film
9, the anneal chamber M4 are used for having perovskite thin film layer to be made annealing treatment to deposition.
Referring to shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6, above-mentioned calcium titanium is utilized the invention also discloses a kind of
Former made of the forming method principle of ore bed film, including tubular housing 2 and conveyer 3,10,11,14 and 22, institute
Conveyer 3,10,11,14 and 22 is stated to be arranged in tubular housing 2.Substrate is respectively arranged with before and after the tubular housing 2 to enter
Enter section M1 and substrate takes out section M5, the tubular housing 2 is disposed with deposit cavity M2, adapter cavity M3 and anneal chamber M4 respectively.
The objective table 7 for placing deposition reactant is provided with the deposit cavity M2, placement annealing is provided with the anneal chamber M4
The objective table 19 of secondary solvent, be also respectively provided with the deposit cavity M2 and anneal chamber M4 barometric control unit 1 and 18 with
And heater 8 and 16.Heater described in M2 makes its distillation to deposition reactant heating in objective table 7, and dress is heated in M4
Put and heating is carried out to the annealing secondary solvent in objective table 19 make its evaporation.Between adjacent segment and chamber and each chamber respectively
Separated using 4,12,15 and 20 dividing plates.The substrate 9 of film to be deposited is placed on frame substrate 24, by conveyer 3,10,11,
14 and 22 since substrate approach section M1, successively continually by deposit cavity M2, adapter cavity M3 and anneal chamber M4 after, finally from base
Piece takes out and takes out the substrate 9 for having deposited calcium titanium ore bed film on section M5 frame substrate 24.
The former is additionally provided with dividing plate control system, the closing of the dividing plate 4,12,15 and 20 and open by every
Panel control system controls.
The conveyer 3,10,11,14 and 22 includes conveyer belt 23.The frame substrate 24 is set on a moving belt.Institute
State the surface that conveyer belt 23 is arranged on objective table 7 and 19, the face objective table 7 and 19 down to be deposited of the substrate 9.
The groove 25 for placing substrate 9 is provided with the middle part of the frame substrate 24, the middle part of groove 25 is provided with recess hole 27.
Groove 25 is slightly larger than substrate 9, and recess hole 27 is slightly less than the surface to be deposited of substrate 9.The face to be deposited of substrate 9 is from recess hole 27
Reveal and be easy to deposit.It is used for admittedly equipped with transversely movable movable substrate fixed plate 26 on the both sides of the frame substrate 24
Determine the position of substrate 9, the substrate fixed plate 26 is fixed on the back side of substrate 9.Recess hole 27 can be according to the tune of the size of substrate 9
Section.The material of the frame substrate 24 can be the nonmetallic materials such as alloy material or glass, ceramics such as stainless steel.
The top of the objective table 7 and 19 is provided with split-flow baffles 6 and 21, on the split-flow baffles 6 and 21 respectively
Multiple tap holes 28 are provided with, the reactant gas that the objective table 7 and 19 evaporates arrives again after split-flow baffles 6 and 21 respectively
Up to the surface of substrate 9.The reactant steam for causing evaporation using split-flow baffles 6 and 21 is uniformly dispersed, so as to obtain homogeneous, repetition
The good perovskite thin film layer of property.Split-flow baffles 6 and 21 can be one or more layers, and tap hole 28 can be circular, square, annular etc.
Shape.
The heater includes the upper heating plate 5 and lower heating plate 8 positioned at deposit cavity M2, and positioned at anneal chamber M4's
Upper heating plate 17 and lower heating plate 16.The upper heating plate 5 of the deposit cavity M2 and anneal chamber M4 upper heating plate 17 fill with transmission
The distance for putting the frame substrate 24 on 10 and 14 distinguishes adjustable, the upper heating plate 5 of the deposit cavity M2 and anneal chamber M4 upper heating
Plate 17 is heated to the substrate 9 on frame substrate 24 respectively, and the lower heating 6 of the deposit cavity M2 and anneal chamber M4 lower heating plate 16 are divided
Do not heated to the annealing secondary solvent in the deposition reactant and objective table 19 in the objective table 7 of place chamber.It is described heavy
Pressure control in product chamber and anneal chamber is 10-5Pa ~105Between Pa；The temperature control of the objective table of the deposit cavity is 100
DEG C ~ 200 DEG C, preferably 120 DEG C ~ 180 DEG C；On the deposit cavity temperature control of heating plate 30 DEG C ~ 150 DEG C, preferably 30
℃~120℃；The temperature control of the objective table of the anneal chamber is at 30 DEG C ~ 120 DEG C, preferably 30 DEG C ~ 80 DEG C；The anneal chamber
Upper temperature of heating plate control is preferably 80 DEG C ~ 120 DEG C at 30 DEG C ~ 200 DEG C.
Deposition reactant in the deposit cavity M2 objective tables 7 is AX, wherein A be in amido, amidino groups or alkali family extremely
Few one kind, preferably methylamino (Methylammonium), ethanamidine base（Formamidinium）Or caesium X is iodine, bromine, chlorine, astatine etc.
The anion of at least one of halogen.Annealing secondary solvent in the anneal chamber M4 objective tables 19 is amide solvent, sulfone
Class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohols solvent, ketones solvent, ether solvent, aromatic hydrocarbon are molten
Any one in agent.
The reaction time of the deposit cavity M2 is controlled in 5min ~ 2h, preferably 10min ~ 60min；The anneal chamber M4 is moved back
Fiery time control is in 5min ~ 2h, preferably 10min ~ 60min.
Gas evaporation speed and semiconductive thin film detection device are additionally provided with the deposit cavity M2 and anneal chamber M4, is used
In the evaporation capacity of control reactant and the film thickness of substrate deposition.
Air bleeding valve 13 is housed at the top of the adapter cavity M3, in row pressure or regulation deposit cavity M2 and anneal chamber M4
Air pressure.
Solvent auxiliary annealing can be carried out in the anneal chamber M4（When placing solvent on objective table 19）It is or solvent-free auxiliary
Help annealing（When not placing solvent on objective table 19）.
It refer to shown in Fig. 6, the invention also discloses a kind of use of the former of calcium titanium ore bed film as the aforementioned
Method, the application method comprise the steps of：
First step, prepare deposition surface and contain precursor BX2Substrate 9；
Second step, deposition there is into precursor BX2Some substrates 9 be positioned on frame substrate 24, open deposit cavity M2 entrance every
Plate 4, the frame substrate 24 with substrate 9 is sent in deposit cavity M2 through substrate approach section M1 by conveyer 3 and 10 carry out it is thin
Film is molded, and that deposit cavity M2 is closed after frame substrate 24 enters deposit cavity M2 enters dividing plate 4；By next batch substrate to be deposited
9 are positioned in another frame substrate 24, are sent in substrate approach section M1 and wait subsequent cycle；
Third step, AX is placed on deposit cavity objective table, the gas pressure in deposit cavity M2 is controlled by barometric control unit 1
Power, gas pressure range 10-5Pa~105Pa；Control the temperature and time of deposit cavity M2 heater so that be positioned over load
AX on thing platform 7, which is heated, is evaporated to gas, AX gas particles and the precursor BX on substrate 92React, generate ABX3Type
Perovskite thin film；
Four steps, deposit cavity M2 discharge dividing plate 12 is opened, the substrate 9 that preceding deposition has perovskite is sent to adapter cavity M3
In, closing deposit cavity M2 discharge dividing plate 12；Deposit cavity M2 entrance dividing plate 4 is opened, another substrate 9 to be deposited is communicated
Device 3 and 10 is sent to deposit cavity M2, carries out third step again, starts another deposition working cycles, implements continuous production；
5th step, that opens anneal chamber M4 enters dividing plate 15, is sent to the substrate 9 of film forming using transmitting device 11 and 14
In anneal chamber M4；Annealing solvent is added on anneal chamber M4 objective table 19 to be annealed；Before being closed after the entrance of frame substrate 24
State dividing plate 15；
6th step, anneal chamber M4 pressure is controlled 10 by barometric control unit 18-5Pa~105A certain value between Pa；Control
A certain value of the temperature of anneal chamber M4 processed heater between 80 DEG C ~ 150 DEG C, the annealing solvent being positioned on objective table 19
It is heated and is evaporated to gas, the ABX on the gas particles auxiliary substrate for solvent of annealing3Type perovskite thin film further crystallizes, and increases
Add film uniformity, complete annealing；
7th step, anneal chamber M4 discharge dividing plate 20 is opened, frame substrate 24 is sent to substrate by conveyer 22 and takes out section M5,
The substrate 9 for having deposited calcium titanium ore bed film is taken out preservation from frame substrate 24, completes the working cycles.
The temperature control of the objective table of the deposit cavity is at 100 DEG C ~ 200 DEG C, preferably 120 DEG C ~ 180 DEG C；The deposition
The temperature control of heating plate is at 30 DEG C ~ 150 DEG C, preferably 30 DEG C ~ 120 DEG C on chamber；The reaction time control of the deposit cavity exists
5min ~ 2h, preferably 10min ~ 60min；The temperature control of the objective table of the anneal chamber is in 30 DEG C ~ 120 DEG C, preferably 30 DEG C
~80℃；Temperature of heating plate control is preferably 80 DEG C ~ 120 DEG C at 30 DEG C ~ 200 DEG C in the anneal chamber；The anneal chamber annealing
Time control is in 5min ~ 2h, preferably 10min ~ 60min.
The invention also discloses a kind of application of the former of foregoing calcium titanium ore bed film, is to be applied to make too
In positive energy battery or LED or thin film field-effect pipe.
Illustrate the concrete application of the present invention with reference to embodiment.
Embodiment 1
It refer to shown in Fig. 7, the application of the former of calcium titanium ore bed film of the invention in area of solar cell is made,
Specifically include following steps：
（1）By 2.5 × 2.5cm ito glass plate successively through liquid detergent, deionized water, acetone, each cleaning of isopropanol ultrasound
30min, then use N2After drying 10min is handled through UV O-zone；
（2）Spin coating PEDOT:PSS, 90 DEG C ~ 150 DEG C drying 5min ~ 20min；
（3）By PbBr2It is dissolved in DMF, concentration 1M, 70 DEG C of stirring 2h, in PEDOT:The spin coating of PSS upper stratas obtains PbBr2It is thin
Film, 70 DEG C ~ 100 DEG C annealing 5min ~ 60min；
（4）Deposition there is into precursor PbBr2One or more pieces substrates 9 be positioned over frame substrate 24, open dividing plate 4, pass through and transmit dress
Put 3 and 10 and be sent to deposit cavity M2 into chamber M1 through substrate, close dividing plate 4；
（5）Dividing plate 12 is opened, by barometric control unit 1 by the Stress control in deposit cavity M2 10-5Pa ~105Between Pa,
Close dividing plate 12；
（6）150 DEG C ~ 200 DEG C of 7 temperature of objective table and upper 80 DEG C ~ 120 DEG C of 5 temperature of heating plate are controlled respectively so that in objective table 7
The evaporation of MABr solvents, the MABr gases of evaporation and the PbBr on substrate 92Film reacts, and generates perovskite thin film, reaction
Time is 5min ~ 30min；
（7）Dividing plate 12 is opened, using air bleeding valve 13 is closed after the row pressure of air bleeding valve 13, deposition is had into perovskite by conveyer 11
The substrate 9 of film is sent to adapter cavity M3, closes dividing plate 12；
（8）Dividing plate 15 is opened, the substrate 9 of film forming is sent to anneal chamber M4 using transmitting device 11 and 14；On objective table 19
Add solvent；Dividing plate 15 is closed, the air pressure in anneal chamber M4 is adjusted by barometric control unit 13, controlled 10-5Pa ~105Pa
Between；Setting the temperature control of objective table 19, the temperature of upper heating plate 17 is 90 DEG C ~ 120 DEG C, is annealed at 60 DEG C ~ 100 DEG C
Processing, annealing time 5min ~ 60min, the thick perovskite thin films of 200nm ~ 350nm are made；
（9）Dividing plate 15 is opened, utilizes closing air bleeding valve 13 after the row pressure of air bleeding valve 13；Dividing plate 15 is closed, dividing plate 20 is opened, will deposit
The substrate for having perovskite thin film is sent to substrate by transmitting device 22 and takes out section, is taken out after the natural cooling of substrate 9, on substrate 9
Deposit electron transfer layer PCBM；
（10）Evaporation metal conductive layer Au electrodes, obtain solar cell.
Fig. 8 is the SEM figures using perovskite thin film made from the equipment of the present invention, can be intuitive to see and pass through from figure
Film crystal even particle size, densification made from such a method, crystallite dimension is in 500nm or so.
Fig. 9 is the XRD of Fig. 8 perovskite thin film, and MAPbBr is only observed in figure3Diffraction maximum and peak type it is sharp, and
Without MABr, PbBr2Diffraction maximum, illustrate that perovskite thin film purity, crystallinity that this method is prepared are higher.
Figure 10 is the Current density-voltage of the perovskite solar cell prepared using the equipment of the present invention（J-V）Curve
Figure, it can be seen that the perovskite solar cell J being preparedscAnd VocHigher, measurement obtains perovskite made from this method too
It is positive can battery photoelectric transformation efficiency up to 15.04%.
Embodiment 2
The former of the calcium titanium ore bed film of the present invention is applied in LED field is made, and specifically includes following steps：
（1）2.5 × 2.5cm FTO PETs plate is surpassed through liquid detergent, deionized water, acetone, isopropanol successively
Sound respectively cleans 20min, then uses N2After drying 15min is handled through UV O-zone；
（2）Spin coating CuSCN, 100 DEG C ~ 200 DEG C drying 5min ~ 20min；
（3）By PbCl2It is dissolved in DMF, concentration 1M, 70 DEG C of stirring 2h, PbCl is obtained in the spin coating of CuSCN upper stratas2Film, 70
DEG C ~ 100 DEG C of annealing 5min ~ 60min；
（4）Deposition there is into precursor PbBr2One or more pieces substrates 9 be positioned over frame substrate 24, open dividing plate 4, pass through and transmit dress
Put 3 and 10 and be sent to deposit cavity M2 into chamber M1 through substrate, close dividing plate 4；
（5）Dividing plate 12 is opened, by barometric control unit 1 by the Stress control in deposit cavity M2 10-5Pa~105Between Pa, close
Close dividing plate 12；
（6）100 DEG C ~ 160 DEG C of 7 temperature of objective table and upper temperature 60 C ~ 120 DEG C of heating plate 5 are controlled respectively so that in objective table 7
The evaporation of MACl solvents, the MACl gases of evaporation and the PbCl on substrate 92Film reacts, and generates perovskite thin film, reaction
5min~30min；
（7）Dividing plate 12 is opened, using air bleeding valve 13 is closed after the row pressure of air bleeding valve 13, deposition is had into perovskite by conveyer 11
The substrate 9 of film is sent to adapter cavity M3, closes dividing plate 12；
（8）Dividing plate 15 is opened, the substrate 9 of film forming is sent to anneal chamber M4 using transmitting device 14；Added on objective table 19
Solvent；Dividing plate 15 is closed, the air pressure in anneal chamber M4 is adjusted by barometric control unit 13, controlled 10-5Pa~105Between Pa；
The temperature control of objective table 19 is set 80 DEG C ~ 120 DEG C of the temperature of upper heating plate 17, to be made annealing treatment at 100 DEG C ~ 160 DEG C,
Annealing time 5min ~ 60min, the thick perovskite thin films of 180nm ~ 320nm are made；
（9）Dividing plate 15 is opened, utilizes closing air bleeding valve 13 after the row pressure of air bleeding valve 13；Dividing plate 15 is closed, dividing plate 20 is opened, will deposit
The substrate for having perovskite thin film is sent to substrate by transmitting device 22 and takes out section, is taken out after the natural cooling of substrate 9, on substrate 9
Deposit electron transfer layer PCBM；
（10）Evaporation metal conductive layer aoxidizes molybdenum electrode, obtains LED.
Embodiment 3
The former of the calcium titanium ore bed film of the present invention is applied in thin film field-effect pipe field is made, and specifically includes following step
Suddenly：
（1）By 2.5 × 2.5cm ito glass plate successively through liquid detergent, deionized water, acetone, each cleaning of isopropanol ultrasound
30min, then use N2After drying 10min is handled through UV O-zone；
（2）Spin coating PEDOT:PSS, 90 DEG C ~ 150 DEG C drying 5min ~ 20min；
（3）By PbBr2It is dissolved in DMF, concentration 1M, 70 DEG C of stirring 2h, in PEDOT:The spin coating of PSS upper stratas obtains PbBr2It is thin
Film, 70 DEG C ~ 100 DEG C annealing 5min ~ 60min；
（4）Deposition there is into precursor PbBr2One or more pieces substrates 9 be positioned over frame substrate 24, open dividing plate 4, pass through and transmit dress
Put 3 and 10 and be sent to deposit cavity M2 into chamber M1 through substrate, close dividing plate 4；
（5）By barometric control unit 1 by the Stress control in deposit cavity M2 10-5Pa~105Between Pa；
（6）150 DEG C ~ 200 DEG C of 7 temperature of objective table and upper 80 DEG C ~ 150 DEG C of 5 temperature of heating plate are controlled respectively so that in objective table 7
The evaporation of MABr solvents, the MABr gases of evaporation and the PbBr on substrate 92Film reacts, and generates perovskite thin film, reaction
5min~30min；
（7）Dividing plate 12 is opened, using air bleeding valve 13 is closed after the row pressure of air bleeding valve 13, deposition is had into perovskite by conveyer 11
The substrate 9 of film is sent to adapter cavity M3, closes dividing plate 12；
（8）Dividing plate 15 is opened, the substrate 9 of film forming is sent to anneal chamber M4 using transmitting device 14；Added on objective table 19
Solvent；Dividing plate 15 is closed, the air pressure in anneal chamber M4 is adjusted by barometric control unit 13, controlled 10-5Pa~105Between Pa；
The temperature control of objective table 19 is set 100 DEG C ~ 150 DEG C of the temperature of upper heating plate 17, to be made annealing treatment at 80 DEG C ~ 100 DEG C,
Annealing time 5min ~ 60min, the thick perovskite thin films of 250nm ~ 420nm are made；
（9）Dividing plate 15 is opened, utilizes closing air bleeding valve 13 after the row pressure of air bleeding valve 13；Dividing plate 15 is closed, dividing plate 20 is opened, will deposit
The substrate for having perovskite thin film is sent to substrate by transmitting device 22 and takes out section, is taken out after the natural cooling of substrate 9, on substrate 9
Deposit electron transfer layer PCBM；
（10）Evaporation metal conductive layer Au electrodes, obtain thin film field-effect pipe.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of forming method of calcium titanium ore bed film, it is characterised in that using a tubular housing, before and after the tubular housing
It is respectively arranged with substrate approach section and substrate takes out section, the tubular housing is respectively arranged with some deposit cavities and/or adapter cavity
And/or anneal chamber, objective table, barometric control unit and heater, institute are respectively arranged with the deposit cavity and anneal chamber
State heater to heat the reactant in objective table, its gas particles, which deposits to, after the reactant heating evaporation is located at
On substrate surface in the chamber, between adjacent segment and chamber and each chamber being utilized respectively dividing plate separates；
The forming method comprises the following steps：The substrate of film to be deposited is placed on frame substrate, by being arranged on tubular cavity
Internal conveyer since substrate approach section, successively continually by some deposit cavities, adapter cavity and anneal chamber after, finally
Taken out from substrate and the substrate for having deposited calcium titanium ore bed film is taken out on the frame substrate of section.
2. existed using former, its feature made of the forming method principle of calcium titanium ore bed film as claimed in claim 1
In, including tubular housing and conveyer, the conveyer be arranged in tubular housing, before and after the tubular housing respectively
Be provided with substrate approach section and substrate and take out section, the tubular housing be respectively arranged with some deposit cavities and/or adapter cavity and/or
Anneal chamber, is provided with the objective table for placing deposition reactant in the deposit cavity, and being provided with placement in the anneal chamber moves back
The objective table of fiery secondary solvent, barometric control unit and heater, institute are also set respectively in the deposit cavity and anneal chamber
State heater respectively to heat the deposition reactant in objective table and annealing secondary solvent, the deposition reactant and move back
After fiery secondary solvent heating evaporation its gas particles deposit to positioned at film to be deposited in the chamber substrate surface on,
Dividing plate is utilized respectively between adjacent segment and chamber and each chamber to separate；The substrate of film to be deposited is placed on frame substrate, by
Conveyer since substrate approach section, successively continually by some deposit cavities and/or adapter cavity and/or anneal chamber after, most
Taken out afterwards from substrate and take out the substrate for having deposited calcium titanium ore bed film on the frame substrate of section.
3. former made of the forming method principle of calcium titanium ore bed film as claimed in claim 2, it is characterised in that institute
Stating conveyer includes conveyer belt, and the frame substrate is set on a moving belt；The conveyer belt is arranged on the surface of objective table,
The face objective table down to be deposited of the substrate.
4. former made of the forming method principle of calcium titanium ore bed film as claimed in claim 3, it is characterised in that
The groove for placing substrate is provided with the middle part of the frame substrate, is provided with recess hole in the middle part of the groove, the groove is bigger
In substrate, the recess hole is slightly less than the surface to be deposited of substrate, and transversely movable work is housed on the both sides of the frame substrate
Dynamic substrate fixed plate is used for the position for fixing substrate, and the substrate fixed plate is fixed on the back side of substrate.
5. former made of the forming method principle of calcium titanium ore bed film as claimed in claim 2, it is characterised in that
The objective table top is provided with split-flow baffles, and multiple tap holes, the objective table evaporation are provided with the split-flow baffles
Reactant gas reach substrate surface again after split-flow baffles.
6. former made of the forming method principle of calcium titanium ore bed film as claimed in claim 2, it is characterised in that institute
Stating heater includes the upper heating plate positioned at deposit cavity and lower heating plate, and the upper heating plate positioned at anneal chamber and lower heating
Plate, the upper heating plate of the upper heating plate and anneal chamber of the deposit cavity is respectively to the substrate heating on frame substrate, the deposit cavity
Lower heating plate and anneal chamber lower heating plate respectively to place chamber objective table in deposition reactant and annealing auxiliary it is molten
Agent is heated；The temperature control of the upper heating plate of the upper heating plate and anneal chamber of the deposit cavity is described at 30 DEG C ~ 150 DEG C
The objective table temperature control of deposit cavity is at 100 DEG C ~ 200 DEG C, and the temperature control of the objective table of the anneal chamber is at 30 DEG C ~ 200 DEG C.
7. former made of the forming method principle of calcium titanium ore bed film as claimed in claim 2, it is characterised in that
Precursor BX is anticipated on the substrate surface of the film to be deposited2, the deposition reactant in the deposit cavity objective table
Molecular structure for the obtained calcium titanium ore bed film of AX, the substrate deposition is ABX3, wherein A is amido, amidino groups or alkali family
At least one of, B be lead, tin, tungsten, copper, zinc, gallium, germanium, arsenic, selenium, rhodium, palladium, silver, cadmium, indium, antimony, osmium, iridium, platinum, gold, mercury,
The cation of at least one of thallium, bismuth, polonium, X are the anion of at least one of iodine, bromine, chlorine, astatine；The anneal chamber loading
Annealing secondary solvent in platform is amide solvent, sulfone class/sulfoxide type solvents, esters solvent, hydro carbons, halogenated hydrocarbon solvent, alcohol
Any one in class solvent, ketones solvent, ether solvent, aromatic hydrocarbon solvent；The reaction time control of the deposit cavity exists
5min ~ 2h, the reaction time of the anneal chamber are controlled in 5min ~ 2h.
8. the application method of the former of calcium titanium ore bed film as claimed in claim 7, it is characterised in that the application method
Comprise the steps of：
First step, prepare deposition surface and contain precursor BX2Substrate；
Second step, deposition there is into precursor BX2Some substrates be positioned on frame substrate, open deposit cavity enter dividing plate, by band
The frame substrate for having substrate is sent in deposit cavity through substrate approach section by conveyer carries out film forming, and it is heavy to treat that frame substrate enters
That deposit cavity is closed after product chamber enters dividing plate；Next batch substrate to be deposited is positioned in another frame substrate, is sent to base
Subsequent cycle is waited in piece approach section；
Third step, AX is placed on deposit cavity objective table, the gas pressure in deposit cavity, gas are controlled by barometric control unit
Body pressure limit is 10-5Pa~105Pa；Control the temperature and time of the heater of deposit cavity so that be positioned on objective table
AX, which is heated, is evaporated to gas, the precursor BX in AX gas particles and substrate2React, generate ABX3Type perovskite thin film；
Four steps, the discharge dividing plate of deposit cavity is opened, the substrate that preceding deposition has perovskite is sent to adapter cavity, it is heavy to close
The discharge dividing plate of product chamber；That opens deposit cavity enters dividing plate, and another communicated device of substrate to be deposited is sent into deposit cavity,
Third step is carried out again, starts another deposition working cycles；
5th step, that opens anneal chamber enters dividing plate, and the substrate of film forming is sent in anneal chamber using transmitting device；
Annealing solvent is added on the objective table of anneal chamber；Aforementioned separator plate is closed after frame substrate entrance；
6th step, the pressure of anneal chamber is controlled 10 by barometric control unit-5Pa~105A certain value between Pa；Anneal chamber
Upper heating plate device a certain value of the temperature between 80 DEG C ~ 150 DEG C；The annealing solvent being positioned on objective table, which is heated, to be steamed
Send out and aid in the ABX on substrate for gas, annealing solvent gas particle3The further reactive crystallization of type perovskite thin film, complete annealing
Processing；
7th step, opens the discharge dividing plate of anneal chamber, and frame substrate is sent to substrate by conveyer and takes out section, having deposited calcium
The substrate of titanium ore layer film takes out preservation from frame substrate, completes the working cycles.
9. the application method of the former of calcium titanium ore bed film as claimed in claim 8, it is characterised in that the deposit cavity
With the pressure control in anneal chamber 10-5Pa~105Between Pa；The temperature control of the objective table of the deposit cavity is 100 DEG C ~ 200
℃；The temperature control of heating plate is at 30 DEG C ~ 150 DEG C on the deposit cavity；The deposit cavity reaction time control 5min ~
2h；The temperature control of the objective table of the anneal chamber is at 30 DEG C ~ 120 DEG C；In the anneal chamber temperature of heating plate control 30 DEG C ~
200℃；The anneal chamber annealing time control is in 5min ~ 2h.
10. a kind of application of the application method of the former of calcium titanium ore bed film as claimed in claim 9, its feature exist
In applied to making solar cell or LED or thin film field-effect pipe.
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| CN201610721611.4A CN107779844A (en) | 2016-08-25 | 2016-08-25 | Forming method, former and its application method of calcium titanium ore bed film and application |
| PCT/CN2017/082793 WO2018036192A1 (en) | 2016-08-25 | 2017-05-03 | Perovskite thin film forming method and forming equipment, method of using forming equipment, and application |
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| CN113471367A (en) * | 2021-06-30 | 2021-10-01 | 无锡极电光能科技有限公司 | System and method for preparing perovskite film layer and application thereof |
| CN113644209A (en) * | 2021-08-11 | 2021-11-12 | 无锡极电光能科技有限公司 | Preparation method and preparation device of perovskite film layer and perovskite solar cell |
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