CN107119256A - A kind of preparation method of tin based perovskites film - Google Patents
A kind of preparation method of tin based perovskites film Download PDFInfo
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000002207 thermal evaporation Methods 0.000 claims abstract description 34
- 238000001704 evaporation Methods 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 43
- 230000008020 evaporation Effects 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000137 annealing Methods 0.000 claims description 27
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- JTDNNCYXCFHBGG-UHFFFAOYSA-L Tin(II) iodide Inorganic materials I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 14
- 239000004408 titanium dioxide Substances 0.000 claims description 13
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical group [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 52
- 238000000034 method Methods 0.000 abstract description 46
- 239000000463 material Substances 0.000 abstract description 41
- 239000010409 thin film Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000012298 atmosphere Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 238000004528 spin coating Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000004886 process control Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 241000143060 Americamysis bahia Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000019552 anatomical structure morphogenesis Effects 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 perovskite Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000002023 wood Substances 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0694—Halides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The present invention is to provide a kind of preparation method of tin based perovskites film, particularly relate to field of compound material, the present invention provides two layers of independent film layer by thermal evaporation, promote the conception interpenetrated of solid film by micro solvent atmosphere, the method of Successful utilization solvent anneal, prepares tin based perovskites film.Methods described can avoid the limitation that solwution method is brought, the reaction that liquid phase can be will be limited to is extended to gas phase field, it can be used on the battery of planar structure, perovskite thin film grain size prepared by methods described can reach more than 4% efficiency in 1 μm of 500nm, perovskite battery prepared by methods described.
Description
Technical field
The present invention relates to field of compound material, it is unleaded that specifically a kind of inorganic material and organic material are combined generation
The method of perovskite material.
Background technology
Solar cell is the device that a kind of utilization photovoltaic effect converts light energy into electric energy.Had since 1839
Since Becquerel has found photovoltaic effect first, solar cell develops very fast in 100 years after
Speed.First generation silica-based solar cell, second generation multi-element compounds thin-film solar cells and the third generation can be substantially divided into
Novel solar battery.Current countries in the world have put into huge manpower and materials in new energy field, especially field of solar energy,
It is considered that solar cell has welcome its golden period, therefore how to develop more inexpensive, more efficient, the life-span is longer
Solar cell is also ensuing challenge.
And in recent years, hydridization perovskite battery is a dark horse in area of solar cell, become most very powerful and exceedingly arrogant
Research object.Within short two year, its peak efficiency has reached more than 22%, and this is that other batteries never occurred
Increasing hold speed, and raw material is also very cheap, and technique is also relatively easy, therefore perovskite solar cell has been sent to thickness
Hope.
But traditional perovskite battery also has the limitation caused by material itself, CH3NH3PbI3Structure cause
Heavy metal lead element either in preparation process, also in use, can all be polluted to environment, therefore, how be reduced
The use of heavy metal element, is also the direction that later Many researchers are groped.Tin of the same clan is a good replacement with lead
Object.But found in groping in a period of time, the perovskite material of tinbase must first antedating response generation calcium titanium in a solvent
Pit wood material can just carry out spin coating, it is impossible to as traditional lead material, can be by PbI2Deng soaking or solution be added dropwise
During with another precursor C H3NH3I (CsI and NH2CHNH2I) react to generate perovskite, because
CH3NH3PbI3In isopropanol (CH3NH3I solvent) solubility is relatively low, and tin based perovskites solubility in isopropanol is higher, very
Easily dissolve so that the material that researcher cannot need.And the method for a step spin coating tin based perovskites, and because tinbase
Perovskite crystalline speed be difficult to control to and with the reason such as substrate contact is bad, often cannot fine and close smooth film, therefore,
Seek it is a kind of preparation method that is smooth and possessing high-quality tin based perovskites can be prepared in planar structure, be instantly non-
Often important research direction.
In conventional perovskite material (CH3NH3PbI3) preparation process in, vapor coating and solvent anneal are all distinguished
High-quality film can be generated.First introduce below prior art prepared in perovskite field by both approaches it is high-quality thin
The successful case of film.
Thermal evaporation refers to substrate to be coated etc. to be placed on the sample stage in vacuum chamber, by thermal evaporation container
Coating Materials is heated, and its atom or molecule is gasified from surface and is escaped, forms steam stream, reach colder substrate surface, so that
Reach the purpose being deposited on substrate.Because being related to the molecule and atom of Coating Materials, the film formed is more uniform
Densification, coverage rate is very high.Early in 2013, Oxonian Snaith professors team just existed《Nature》Published on magazine
With the method for thermal evaporation plated film it is prepared for high-quality leaded CH3NH3PbI3Work.(Liu M, Johnston MB,
Snaith HJ.Efficient planar heterojunction perovskite solar cells by vapour
Deposition [J] .Nature, 2013,501 (7467)：395-398.)
Solvent anneal is such a independent into for membrane meanses, being more that an auxiliary improves thin relative to thermal evaporation
The method of film pattern, this is by the case where forming film, by solvent atmosphere, in heating process, by film
Redissolution and crystallization, form bigger crystal grain and more excellent film morphology.In Nebraska,USA university woods in 2014
The Huang Jingsong professors team for agreeing branch school exists《Advanced Materials》On published correlation work, with normal spin coating system
Standby perovskite thin film contrast, the CH handled by solvent anneal3NH3PbI3Perovskite thin film possesses bigger crystal grain, as
The device performance that basis is worked it out is also more excellent.(Xiao Z, Dong Q, Bi C, et al.Solvent Annealing of
Perovskite-Induced Crystal Growth for Photovoltaic-Device Efficiency
Enhancement [J] .Advanced Materials, 2014,26 (37)：6503-6509.)
Generally in CH3NH3PbI3Preparation method except thermal evaporation described above, main or solution spin-coating method is
It is main.Solution spin-coating method is roughly divided into two kinds, and the first major class is referred to as a step spin-coating method, as its name suggests, first generates reaction
CH3NH3PbI3PbI2And CH3NH3I is first dissolved in solvent, for example dimethylformamide (DMF) or dimethyl sulfoxide (DMSO)
(DMSO) in, by sol evenning machine by solution spin coating, film forming of annealing, you can obtain perovskite thin film；Second major class is referred to as continuous molten
Liquid sedimentation, this is by PbI2And CH3NH3I is divided to the method for carrying out film forming for two steps, for example, can be by PbI2It is dissolved in DMF, passes through
Spin coating, first by PbI2It is deposited on substrate, solvent is volatilized by annealing, then again by CH3NH3I is dissolved in isopropanol, will be molten
Drop, which is added in, deposited PbI2Substrate on or the substrate is immersed in isopropanol so that PbI2And CH3NH3I reacts, raw
Into perovskite.But above is the main flow preparation method of traditional leaded perovskite, tin based perovskites prepared by the present invention are thin
Membrane material, due to its particularity, property is relative to CH3NH3PbI3It is more unstable, and it is easy to molten in aqueous isopropanol
Solution, therefore become the big obstacle that the current field prepares tin based perovskites, many work can only all use the first step
The method of spin coating prepares CH3NH3SnI3.Kanatzidis professors team early in Northwestern Univ USA in 2014 exists《Nature
Photonics》Work (Hao F, Stoumpos C C, Cao D H, the et al.Lead-free solid-state of upper publication
Organic-inorganic halide perovskite solar cells [J] .Nature Photonics, 2014,8
(6)：489-494.), be earliest it is a collection of pure tin based perovskite is prepared to the article for applying to photoelectric device, while the work
What is used is a step solwution method, while follow-up many work are all to be improved based on this, then can not all walk out solution
The limitation of method, while pattern is all not very good, obtained perovskite is all island or discontinuous film.
The content of the invention
Liquid phase reactor can be avoided so as to the method for preparing high-quality thin film it is an object of the invention to provide a kind of, and energy
Reduce the limitation that substrate pattern is brought.The method that current field prepares tin based perovskites solar cell is confined to solwution method,
Because tin based perovskites solution and poriferous titanium dioxide (solar cell substrate material) wellability are bad, generally require to add it
His material auxiliary film forming needs to use anti-solvent and enables perovskite solution solute when spin coating to accelerate precipitation, this
A little experimental methods often bring new impurity, and ratio control is improper to be formed phase separation or cause operation excessively cumbersome, right
Inhibition is played in experiment process.And the method that provides of the present invention, whole operation includes two important steps and is respectively：Before
Drive the thermal evaporation deposition of thing and the generation of film is realized by solvent anneal, the invention effectively increases conventional efficient, and
And to possess material pure for the film prepared, crystallite dimension is big, and efficiency of light absorption is high, the features such as optics excellent performance.
The method therefore is applied to tinbase calcium titanium by the mode based on thermal evaporation plated film in the Successful utilization of lead-based perovskite
Ore deposit is a good idea, but passes through experiment and find, reactant ratio or reaction rate are adjusted anyway, all can not be real
Impurity is very more in the complete generation of existing perovskite, obtained product, and this reality is taught that, only the method for thermal evaporation
Tin based perovskites can not independently be obtained.Therefore it is proposed that thermal evaporation provides two layers of independent film layer, by micro molten
Agent atmosphere promotes the conception interpenetrated of solid film, and the method for Successful utilization solvent anneal broken tin based perovskites
The limitation that can only be prepared with liquid phase reactor, therefore it is that of the invention one is big that tin based perovskites are prepared by new means
Bright spot.
Meanwhile, the structural order of perovskite battery is typically FTO, compact titanium dioxide, poriferous titanium dioxide, perovskite,
Hole transmission layer, electrode.Porous titanium dioxide effect generally can for transmission electronics, and loose structure can increase with
The contact surface area of perovskite so that electronics is easier to inject titanium dioxide, and because tin based perovskites material from calcium titanium ore bed
Contact of the material with compact titanium dioxide in itself is bad, so the essentially all of work on tin based perovskites is all porous
Prepared on the basis of titanium dioxide, but a layer device structure of doing then means increase and the experimental implementation of cost more
It is more cumbersome, and poriferous titanium dioxide needed by high annealing, and this is the big factor that obstruction prepares flexible device, and this
Invention can by the method for thermal evaporation, by perovskite material on compact titanium dioxide Direct precipitation (fine and close titanium dioxide
Available for the battery for preparing planar heterojunction), the problem of so avoiding solution and bad substrate wellability is not influenceing device
Under the behavior pattern of part, device architecture is simplified, and the film also more smooth densification of predecessor that thermal evaporation is obtained, it is follow-up
Reaction provide more preferable condition.
By the comparison for thermal evaporation and solwution method, thermal evaporation can be with the less limitation for avoiding substrate so that material
It can be attached in more smooth fine and close form on substrate, this method is by the method for substep thermal evaporation, by SnI2(SnBr2)
And CH3NH3I (CsI, NH=CHNH3I and CH3CH2NH3I) successively evaporation arrives fine and close TiO2On, and the temperature remains within the normal range, it is ensured that
Predecessor can be deposited on substrate, because temperature is relatively low, effectively reduce reacting to each other for two kinds of predecessors, this is and lead base calcium
The mode of thermal evaporation is different in titanium ore, and mode reported in the literature is desirable to allow in the case of double source thermal evaporation simultaneously
PbI2And CH3NH3I fully reacts, and obtains perovskite thin film, and in the present invention, and the purpose of thermal evaporation is to allow SnI2(SnBr2)
And CH3NH3I (CsI, NH=CHNH3I and CH3CH2NH3I) it is individually present in the form of a film, it is meant that now both do not occur also
Reaction, is separate double-layer filmses.By solvent anneal, to reach the purpose of reaction.Lead-based perovskite is used before this
The meaning of solvent anneal be that, in the case where having formed lead-based perovskite, solvent atmosphere causes the further molten of perovskite
Solution and recrystallization, enabling to the crystal grain of perovskite can become big, reduce crystal boundary, further be carried as reduction in optics
The compound guarantee of stream.And in the present invention, solvent anneal is not the booster action of a raising crystal mass, but promote anti-
The core procedure answered, a small amount of solvent atmosphere can accelerate SnI2(SnBr2) and CH3NH3I (CsI, NH=CHNH3I and
CH3CH2NH3I) two layers solid film is interpenetrated, by micro dissolving, and lower to provide two kinds of materials mutual microcosmic by DMF
The chance of contact so that two kinds of materials are fully contacted, and greatly promote reaction, by the control of temperature and dosage, can be caused molten
The infiltration and volatilization of agent reach a balance, in dynamic equilibrium, and crystal grain, which is constantly formed, grows up, the perovskite thin film finally obtained
100% coverage rate is reached, the particle diameter of perovskite crystal grain is between 500nm-1 μm, and perovskite thin film thickness is 400nm.Fig. 7, Fig. 8
The property of material is then demonstrated, the perovskite material really required for us.
In the present invention, equipment is used for the vacuum coating equipment and upper that glove box of dried shrimps Cairo of Shenyang scientific instrument
Assembling combination, is conducive to a whole set of experimental implementation to be completed under inert gas shielding.
A kind of preparation method of tin based perovskites film, its step is as follows：
(1) substrate prepares：
It is put into after substrate cleaning standby in plated film instrument vacuum chamber；Described substrate is fluorine doped tin oxide (FTO), densification two
Titanium oxide, silicon chip, glass, poriferous titanium dioxide, aluminum oxide, zirconium oxide；
(2) thermal evaporation：
Operating process is carried out under inert gas shielding.
By circulating water, by the temperature control of recirculated water in 15-20 DEG C, thermal evaporation vacuum：3×10-4-6×10-4Pa
By inorganic matter SnX2Powder is put into evaporation of metal boat, and evaporation current is 35A-47A, and evaporation rate arrives for 2nm/s
4nm/s, deposits SnX2Film, described X is halogen；
AX powder is added in crucible or evaporation of metal boat, 50-100 DEG C of evaporating temperature of control or evaporation current 42-45A,
Evaporation rate 2nm/s to 4nm/s is kept, AX films are deposited, described A is ion or cesium ion containing ammonium root, and described X is halogen
Race's element；
(3) solvent anneal：
Operating process is carried out under inert gas shielding.
SnX2It is 1.2: 1-2.5: 1 with AX film thicknesses ratio, is positioned on the warm table preheated in advance, is preheated,
Annealing solvent is added on culture dish, by culture dish left-hand thread in SnX2Can film forming with annealing on AX films.
Evaporation of metal boat described in described step (2) is tantalum boat, and electric current is 35-40A；Evaporation of metal boat is molybdenum boat, electricity
Flow for 44-47A；Evaporation of metal boat is tungsten boat, and electric current is 42-45A.
SnX described in described step (2)2For SnI2And SnBr2。
AX described in described step (2) is CsI, CH3NH3I, NH=CHNH3I、CH3CH2NH3One kind in I.
Solvent selection DMF (DMF) or dimethyl sulfoxide (DMSO) (DMSO) or γ-fourth in described step (3)
Lactone (GBL).
DMF consumption is 3-7 μ L in described step (3).Heretofore described solvent anneal process,
Solvent is used for DMF, quantity of solvent is maintained at 120-150 DEG C in 3-7 μ L, annealing temperature.
120-150 DEG C of annealing temperature in described step (3), the time is 5-10min.
Thermal evaporation and solvent anneal process are in inert gas (Ar, N in the present invention2) the lower progress of protection.
Heretofore described evaporation coating is cooled by circulation, and temperature control is at 15-20 DEG C.
SnI in the present invention2Thickness range is controlled in 200-250nm, CH3NH3I thickness controls in 150-200nm, generation
Perovskite thin film thickness is 400nm or so.
In the present invention, the particle diameter of perovskite crystal grain refers to：In the electron scanning micrograph of perovskite material top view, calcium
The external diameter of a circle of titanium ore crystal grain.
In the present invention, the thickness control of perovskite material can pass through SnI2And CH3NH3I evaporation time and evaporation speed
Degree is controlled, the particle diameter of perovskite crystal grain can by solvent anneal when annealing temperature and solvent strength control.
In the present invention, perovskite thin film thickness refers to：In the electron scanning micrograph of perovskite material cross section, substrate
Perovskite material thickness above.
Beneficial effect
The composite of the present invention has higher absorptivity, and absorption efficiency is in short-wave band 90% or so, and this is just protected
Absorbing for most of light has been demonstrate,proved, an essential condition of photoelectric device is used as.
1. the composite of the present invention has higher photoluminescence intensity, the band gap of tin based perovskites is 1.3eV, correspondence
Absorption cut-off band edge be 930nm or so, from the point of view of Fig. 8 PL data, corresponding emission peak is exactly 930nm, therefore is had very
Good matching degree, coincide with existing literature data.
2. the composite of the present invention has in good flatness, Fig. 4 as can be seen that film is made up of crystal grain, micro-
Under metrical scale, flatness is all very good, and this is conducive to contacting with hole transmission layer, reduces the Carrier recombination in interface；
3. the present invention can apply to the perovskite material of tinbase in planar structure, such benefit is can be by calcium titanium
Ore deposit film is made on many substrates, is prepared similar to PET etc. on the substrate of flexible device, and other are used for testing the lining of sign
Bottom is first-class；
4. the present invention have environment-friendly, cost it is low, it is easy prepare, can one or more advantages such as mass production, pass
Perovskite device prepared by the solwution method of system, it is necessary to operate, and can then be made in batches during prepared by thermal evaporation piecewise
It is standby, at the same solvent anneal process can also multi-disc film-substrate handled together, greatly save preparation cost and simplification
Preparation process.
Brief description of the drawings
Accompanying drawing described herein is used for providing a further understanding of the present invention, constitutes the part of the application.Attached
In figure：
Fig. 1 is the poor CH of the direct pattern obtained from solution spin coating3NH3SnI3The SEM of material
Photo.Because contact of the perovskite material with substrate is bad, it is easy to form the block film of island.
The SnI that Fig. 2 completes for evaporation2And CH3NH3The photo of the SEM of I bilayer films.Now optics shines
Piece shows purple, and two kinds of materials have occurred and that hair is answered, but reaction is carried out not exclusively, and surface, which can be seen, fine crystals generation.
The SnI that Fig. 3 completes for evaporation2And CH3NH3The electron scanning micrograph in I bilayer films section.In interface
The layering of clearly two kinds of materials can be seen.
Fig. 4 is the CH after being handled by solvent anneal3NH3SnI3The photo of the SEM of film.From Fig. 2's
The random morphogenesis crystal grain of large scale, and flatness is very high, and defect is also seldom.
Fig. 5 is the CH after being handled by solvent anneal3NH3SnI3The photo of the SEM of film sections.Can
Block crystal grain is clearly apparent, titanium dioxide and hole transmission layer can be directly connected, it is brilliant in crystal that big crystal grain can reduce carrier
It is compound at boundary, improve electric property.
Fig. 6 is the CsSnI after being handled by solvent anneal3The photo of the SEM of film.
Fig. 7 is SnI2And CH3NH3I bilayer film is handled to ultimately producing calcium titanium by solvent anneal from original state
The X-ray diffraction spectrum of ore deposit film.From initial SnI2And CH3NH3I and perovskite signal exist simultaneously, with solvent anneal mistake
The progress of journey, to last SnI2And CH3NH3I is wholly absent, only the signal of remaining perovskite.
Fig. 8 is the CH after being handled by solvent anneal3NH3SnI3The photoluminescence spectrum of film.The corresponding wavelength of glow peak is just
It is well 930nm, with CH3NH3SnI3Band gap 1.3eV it is consistent.
Fig. 9 is the CH after being handled by solvent anneal3NH3SnI3The solar cell that film is made efficiency chart (electric current-
Voltage curve).Battery peak efficiency can reach more than 4%.
Figure 10 is the CH after being handled by solvent anneal3NH3SnI3The solar cell that film is made is under burning voltage
Electric current changes over time curve, sign be device stability.Illumination can be carried out at constant pressure, in prolonged situation
Under, electric current can be maintained at steady state value, illustrate that material is not decomposed, highly stable.
Embodiment
Embodiment 1
(1) substrate prepares：
Diisopropoxy bis-acetylacetonate titanium solution is mixed according to 1: 8 volume ratio with isopropanol, is sprayed on substrate,
Spraying frequency is 2 times/min, and the substrate prepared is positioned in vacuum chamber by 500 DEG C of annealing；
(2) thermal evaporation：
Operating process is carried out under nitrogen protection.
By circulating water, by temperature control in 15 DEG C, thermal evaporation vacuum：3×10-4Pa
By SnI2Powder is put into tungsten boat, controls evaporation current, is controlled in 42A.Evaporation rate 3nm/s, obtains SnI2It is thin
Film, thickness is 250nm；
By CH3NH3I powder is added in crucible, controls 70 DEG C of evaporating temperature, evaporation rate 4nm/s, whole-process control temperature 65-
75 DEG C, thickness is 150nm.Front and section are as shown in Figures 2 and 3.
SnI is deposited on substrate2And CH3NH3I, sample needed for being.
(3) solvent anneal：
Operating process is carried out under nitrogen protection.
Sample is taken out, substrate surface film is in purple, the transparent aobvious brownish black of glass surface is positioned over and is warming up to 130 in advance
DEG C warm table on, carry out preheating 1min, sample surfaces are rapidly by purple blackening, and this is that two kinds of material inter-diffusion reactions are caused
Phenomenon.
5 μ L DMF is added dropwise on diameter 10cm, height 1.5cm culture dish, by culture dish left-hand thread on sample, protects
130 DEG C of annealing temperature is held, annealing 10min can film forming；Front and section are as shown in Figure 4 and Figure 5.
Embodiment 2
(1) substrate prepares：
20% oxidation tin colloid is mixed with water according to 1: 6 volume ratio, is spin-coated on substrate, rotating speed 3000r/min,
150 DEG C of annealing, the substrate prepared is positioned in vacuum chamber；
(2) thermal evaporation：
Operating process is carried out under nitrogen protection.
By circulating water, by temperature control in 15 DEG C, thermal evaporation vacuum：3×10-4Pa
By SnI2Powder is put into tungsten boat, controls evaporation current, is controlled in 42A.Evaporation rate 3nm/s, obtains SnI2It is thin
Film, thickness is 250nm；
CsI powder is added in tungsten evaporation boat, evaporation current 43A is controlled, evaporation rate 3nm/s, whole-process control temperature is thick
Spend for 100nm；
SnI is deposited on substrate2And CsI, sample needed for being.
(3) solvent anneal：
Operating process is carried out under nitrogen protection.
Sample is taken out, is positioned over and is warming up in advance on 150 DEG C of warm table, preheating 1min is carried out, sample surfaces are rapid
By purple blackening, this is the phenomenon that two kinds of material inter-diffusion reactions are caused.
3 μ L DMF is added dropwise on diameter 10cm, height 1.5cm culture dish, by culture dish left-hand thread on sample, protects
150 DEG C of annealing temperature is held, annealing 10min can film forming.As shown in Figure 6
Embodiment 3
(1) substrate prepares：
18NR-T colloidal tio 2 is mixed with ethanol according to 1: 3 mass ratio, is spin-coated on substrate, rotating speed is
4000r/min, 500 DEG C of annealing, the substrate prepared is positioned in vacuum chamber；
(2) thermal evaporation：
Operating process is carried out under argon gas protection.
By circulating water, by temperature control in 15 DEG C, thermal evaporation vacuum：3×10-4pa
By SnBr2Powder is put into tungsten boat, controls evaporation current, is controlled in 40A.Evaporation rate 3nm/s, obtains SnBr2It is thin
Film, thickness is 200nm；
By CH3NH3I powder is added in crucible, controls 70 DEG C of evaporating temperature, and evaporation rate 3nm/s, whole-process control temperature is thick
Spend for 100nm；
SnBr is deposited on substrate2And CH3NH3I, sample needed for being.
(3) solvent anneal：
Operating process is carried out under argon gas protection.
Sample is taken out, is positioned over and is warming up in advance on 150 DEG C of warm table, preheating 1min is carried out, sample surfaces are rapid
By purple blackening, this is the phenomenon that two kinds of material inter-diffusion reactions are caused.
5 μ L DMSO is added dropwise on diameter 10cm, height 1.5cm culture dish, by culture dish left-hand thread on sample, protects
120 DEG C of annealing temperature is held, annealing 10min can film forming.
Embodiment 4
(1) substrate prepares：
Titanium isopropoxide solution is mixed according to 1: 3 mass ratio with ethanol, is spin-coated on glass, rotating speed 4000r/min,
500 DEG C of annealing, the substrate prepared is positioned in vacuum chamber；
(2) thermal evaporation：
Operating process is carried out under argon gas protection.
By circulating water, by temperature control in 20 DEG C, thermal evaporation vacuum：6×10-4Pa
By SnI2Powder is put on tantalum boat, controls evaporation current, is controlled in 37A.Evaporation rate 3nm/s, obtains SnI2It is thin
Film, thickness is 250nm；
By NH=CHNH3I powder is added in crucible, controls 75 DEG C of evaporating temperature, evaporation rate 3nm/s, whole-process control 70-
80 DEG C, thickness is 150nm；
SnI is deposited on substrate2And NH=CHNH3I, sample needed for being.
(3) solvent anneal：
Operating process is carried out under argon gas protection.
Sample is taken out, is positioned over and is warming up in advance on 140 DEG C of warm table, preheating 1min is carried out, sample surfaces are rapid
By purple blackening, this is the phenomenon that two kinds of material inter-diffusion reactions are caused.
7 μ L DMF is added dropwise on diameter 10cm, height 1.5cm culture dish, by culture dish left-hand thread on sample, protects
140 DEG C of annealing temperature is held, annealing 10min can film forming.
Embodiment 5
(1) substrate prepares：
Butyl titanate is mixed according to 1: 3 mass ratio with ethanol, is spin-coated on glass, rotating speed 4000r/min, 500
DEG C annealing, the substrate prepared is positioned in vacuum chamber；
(2) thermal evaporation：
Operating process is carried out under argon gas protection.
By circulating water, by temperature control in 20 DEG C, thermal evaporation vacuum：4×10-4Pa
By SnI2Powder is put on molybdenum boat, controls evaporation current, is controlled in 45A.Evaporation rate 3nm/s, obtains SnI2It is thin
Film, thickness is 250nm；
By CH3CH2NH3I powder is added in crucible, controls 80 DEG C of evaporating temperature, evaporation rate 4nm/s, whole-process control temperature
75-90 DEG C, thickness is 120nm；
SnI is deposited on substrate2And CH3CH2NH3I, sample needed for being.
(3) solvent anneal：
Operating process is carried out under argon gas protection.
Sample is taken out, is positioned over and is warming up in advance on 140 DEG C of warm table, preheating 1min is carried out, sample surfaces are rapid
By purple blackening, this is the phenomenon that two kinds of material inter-diffusion reactions are caused.
5 μ L GBL is added dropwise on diameter 10cm, height 1.5em culture dish, by culture dish left-hand thread on sample, protects
140 DEG C of annealing temperature is held, annealing 10min can film forming.
Claims (7)
1. a kind of preparation method of tin based perovskites film, it is characterised in that：
（1）Substrate prepares：
It is put into after substrate cleaning standby in plated film instrument vacuum chamber;Described substrate is fluorine doped tin oxide（FTO）, fine and close dioxy
Change titanium, silicon chip, glass, poriferous titanium dioxide, aluminum oxide, zirconium oxide；
（2）Thermal evaporation：
Under inert gas shielding, by circulating water, the temperature control of bad water is followed in 15-20 DEG C, thermal evaporation vacuum：3
×10-4-6×10-4Pa；
By inorganic matter SnX2Powder is put into evaporation of metal boat, and evaporation current is 35A-47A, and evaporation rate is 2nm/s to 4nm/s,
Deposit SnX2Film, described X is halogen；
AX powder is added in crucible or evaporation of metal boat, 50-100 DEG C of evaporating temperature of control or evaporation current 42-45A are kept
Evaporation rate 2nm/s to 4nm/s, deposits AX films, and described A is ion or cesium ion containing ammonium root, and described X is halogen family member
Element；
（3）Solvent anneal：
Under inert gas shielding, SnX2It is 1.2 with AX film thicknesses ratio:1—2.5:1, it is positioned over the warm table preheated in advance
On, preheated, annealing solvent is added on culture dish, by culture dish left-hand thread in SnX2Can be into annealing on AX films
Film.
2. preparation method according to claim 1, it is characterised in that：Described step（2）Described in evaporation of metal boat be
Tantalum boat, electric current is 35-40A；Evaporation of metal boat is molybdenum boat, and electric current is 44-47A；Evaporation of metal boat is tungsten boat, and electric current is 42-
45A。
3. preparation method according to claim 1, it is characterised in that：Described step（2）Described in SnX2For SnI2With
SnBr2。
4. preparation method according to claim 1, it is characterised in that：Described step（2）Described in AX be CsI,
CH3NH3I、NH=CHNH3I、CH3CH2NH3One kind in I.
5. preparation method according to claim 1, it is characterised in that：Described step（3）Middle solvent selects N, N- diformazans
Base formamide（DMF）Or dimethyl sulfoxide (DMSO)（DMSO）Or gamma-butyrolacton（GBL）.
6. preparation method according to claim 5, it is characterised in that：Described step（3）Middle N,N-dimethylformamide
Consumption is 3-7 μ L.
7. preparation method according to claim 1, it is characterised in that：Described step（3）Middle annealing temperature 120-150
DEG C, the time is 5-10min.
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| CN107742661A (en) * | 2017-10-19 | 2018-02-27 | 辽宁科技大学 | The method that inorganic tin based perovskites solar cell is prepared with physical vaporous deposition |
| CN112106219A (en) * | 2018-03-20 | 2020-12-18 | 国立大学法人京都大学 | Method for manufacturing tin-based perovskite layer and solar cell |
| CN112397653A (en) * | 2020-11-17 | 2021-02-23 | 山东大学 | Efficient and stable inorganic lead-free perovskite solar cell and preparation method thereof |
| CN112647047A (en) * | 2020-12-02 | 2021-04-13 | 河南大学 | Preparation method and application of cesium tin iodine film |
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| CN104733618A (en) * | 2015-03-06 | 2015-06-24 | 中国科学院大学 | Method for preparing perovskite solar cell absorption layer |
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| CN106463625A (en) * | 2014-05-05 | 2017-02-22 | 学校法人冲绳科学技术大学院大学学园 | System and method for fabricating perovskite film for solar cell applications |
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| CN112397653A (en) * | 2020-11-17 | 2021-02-23 | 山东大学 | Efficient and stable inorganic lead-free perovskite solar cell and preparation method thereof |
| CN112397653B (en) * | 2020-11-17 | 2023-04-18 | 山东大学 | Efficient and stable inorganic lead-free perovskite solar cell and preparation method thereof |
| CN112647047A (en) * | 2020-12-02 | 2021-04-13 | 河南大学 | Preparation method and application of cesium tin iodine film |
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