CN107123741A - The CsPbBr3 photovoltaic cells and its manufacture method of a kind of phthalocyanine dye sensitization - Google Patents
The CsPbBr3 photovoltaic cells and its manufacture method of a kind of phthalocyanine dye sensitization Download PDFInfo
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- 239000001007 phthalocyanine dye Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 26
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 24
- 230000008313 sensitization Effects 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 230000005540 biological transmission Effects 0.000 claims abstract description 35
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 230000027756 respiratory electron transport chain Effects 0.000 claims abstract description 26
- 238000012986 modification Methods 0.000 claims abstract description 20
- 230000004048 modification Effects 0.000 claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000001771 vacuum deposition Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 9
- 235000004237 Crocus Nutrition 0.000 claims description 8
- 241000596148 Crocus Species 0.000 claims description 8
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 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 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 PolyTPD Chemical compound 0.000 claims description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 4
- 239000006193 liquid solution Substances 0.000 claims description 4
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 claims description 3
- XDXWNHPWWKGTKO-UHFFFAOYSA-N 207739-72-8 Chemical compound C1=CC(OC)=CC=C1N(C=1C=C2C3(C4=CC(=CC=C4C2=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC(=CC=C1C1=CC=C(C=C13)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)N(C=1C=CC(OC)=CC=1)C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 XDXWNHPWWKGTKO-UHFFFAOYSA-N 0.000 claims description 3
- 229910015711 MoOx Inorganic materials 0.000 claims description 3
- 229920001167 Poly(triaryl amine) Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000005368 silicate glass Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000005361 soda-lime glass Substances 0.000 claims description 3
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 2
- 230000005525 hole transport Effects 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910021389 graphene Inorganic materials 0.000 claims 1
- 238000009738 saturating Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 43
- 230000001235 sensitizing effect Effects 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/16—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering
- H10K71/164—Deposition of organic active material using physical vapour deposition [PVD], e.g. vacuum deposition or sputtering using vacuum deposition
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/311—Phthalocyanine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to inorganic perovskite CsPbBr3 film photovoltaic cell technical fields, and in particular to the CsPbBr3 film photovoltaic cells and its manufacture method of a kind of phthalocyanine dye sensitization.The CsPbBr3 photovoltaic cells of described phthalocyanine dye sensitization include electrically conducting transparent substrate, hole transmission layer, CsPbBr3 films photosensitive layer, dye-sensitized layer, electron transfer layer, electrode modification layer and reflecting electrode and constituted.The present invention can improve energy conversion efficiency and the life-span of CsPbBr3 photovoltaic cells.
Description
Technical field
The present invention relates to inorganic perovskite CsPbBr3 photovoltaic cell technical fields, and in particular to a kind of phthalocyanine dye sensitization
CsPbBr3 photovoltaic cells and its manufacture method.
Background technology
Energy crisis and environmental pollution are the two big outstanding problems that mankind nowadays social development faces.With solar cell
Electric energy is directly converted solar energy into for the photovoltaic industry of core, is one of utilizable energy most cleaned of the current mankind,
It is generally acknowledged " green energy resource ".In recent years, the research boom of the perovskite solar cell swept from field of solar energy is caused
The attention of increasing scientific research personnel, this kind of perovskite material has excellent photoelectric properties, and such as quantum efficiency is high, and light is inhaled
Receive coefficient big, carrier mobility distance etc., along with its solution processable.Perovskite has been shown invariably to lead in solar energy
Huge application prospect in domain.Conventional perovskite material is mainly organic inorganic hybridization perovskite (CH3NH3PbX3) at present,
One of such material is that thermal stability is poor the problem of very big, and material is easily decomposed at high temperature.Inorganic perovskite CsPbBr3
This problem can be avoided, it can bear more than 200 DEG C of high temperature.
But inorganic perovskite CsPbBr3 photovoltaic cells are also and imperfect.At present, the problem of CsPbBr3 batteries are present master
Have：(1) research of CsPbBr3 batteries is at the early-stage in the world, the CsPbBr3 thin film surface planenesses particularly prepared lack
Fall into, there is substantial amounts of hole, the presence of these holes can cause the electron transfer layers such as C60 and the direct of hole transmission layer to connect
Touch, increase the recombination probability of electron hole, reduce the parallel resistance of battery, cause the short circuit current flow of battery, fill factor, curve factor and open
Comprehensive decline of the characterisitic parameters such as road voltage, so as to reduce the efficiency of battery.(2) CsPbBr3 light abstraction width is in 300-
Within the scope of 520 nm, absorb weaker in 520-760 nm visible-range and near infrared region or almost do not absorb,
Which greatly limits the photoelectric current of CsPbBr3 batteries and cell power conversion efficiency.(3) CsPbBr3 batteries are also existed in addition
CsPbBr3 is sensitive to water oxygen, the problem of influenceing its life-span.Property of the problem of the solving this several respect for raising CsPbBr3 batteries
Can be very urgent.
The content of the invention
In order to solve problem present in CsPbBr3 photovoltaic cells in background technology, the invention provides a kind of phthalocyanine dye
Expect CsPbBr3 photovoltaic cells of sensitization and preparation method thereof, the technical scheme of use is as follows：
As one aspect of the present invention, there is provided the CsPbBr3 photovoltaic cells that a kind of phthalocyanine dye is sensitized, it is characterised in that bag
Include electrically conducting transparent substrate, hole transmission layer, CsPbBr3 films photosensitive layer, dye-sensitized layer, electron transfer layer, electrode modification layer
Constituted with reflecting electrode.
Further, described CsPbBr3 films photosensitive layer is CsPbBr3 polycrystalline, is formed on hole transmission layer,
The surface Root Mean Square roughness of CsPbBr3 film photosensitive layer thickness 100-300 nm, CsPbBr3 film photosensitive layers is 20-40
nm。
Further, described dye-sensitized layer is phthalocyanine dye, and dye-sensitized layer formation is in CsPbBr3 film photosensitive layers
On, described dye-sensitized layer is preferably SubPc, ClAlPc, SubNc, thickness 10-20 nm.
Further, described electrically conducting transparent substrate is made a living the quartz glass with ITO, silicate glass, high silica glass
The clear glass such as glass or soda-lime glass, the ITO thickness is preferably 100-300 nm, and light transmittance is more than 85%, and square resistance is small
In 10 Ω.
Described hole transmission layer formation is on electrically conducting transparent substrate, and described hole transmission layer includes but is not limited to stone
Black alkene, PEDOT:PSS, PTAA, polyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE, PEI, it is empty
Cave transport layer thickness is preferably 10-50 nm.
Further, the CsPbBr3 photovoltaic cells of described phthalocyanine dye sensitization, it is characterised in that described electronics is passed
Defeated layer formation is on dye-sensitized layer, and described electron transfer layer includes but is not limited to C60, C70, PCBM, electron transfer layer
Thickness is preferably 20-50 nm.
Further, described electrode modification layer is one kind in BCP, Bphen, Alq3, TPBI, and preferred thickness is 5-10
nm。
Further, the formation of described reflecting electrode is on electrode modification layer, and described reflecting electrode includes but do not limited
In Al, Au, Ag, the preferred thickness 100-1000 nm of reflecting electrode.
A kind of manufacturer for the CsPbBr3 photovoltaic cells being sensitized as another aspect of the present invention there is provided phthalocyanine dye
Method, it is characterised in that the preparation of device sequentially includes step successively：
(1) electrically conducting transparent substrate is cleaned；
(2) hole transmission layer is formed in electrically conducting transparent substrate；
(3) CsPbBr3 film photosensitive layers are formed on hole transmission layer；
(4) dye-sensitized layer is formed on CsPbBr3 film photosensitive layers；
(5) electron transfer layer is formed on dye-sensitized layer；
(6) electrode modification layer is formed on the electron transport layer；
(7) reflecting electrode is formed on electrode modification layer.
Further, a kind of manufacture method of the CsPbBr3 photovoltaic cells of described phthalocyanine dye sensitization, its feature exists
In formation CsPbBr3 films photosensitive layer includes step on hole transmission layer：
(1) CsPbBr3 polycrystalline is synthesized；
(2) CsPbBr3 precursor solutions are configured, before the concentration of the CsPbBr3 precursor solutions is 0.5 M, the CsPbBr3
CsPbBr3 polycrystalline of the solute of liquid solution for synthesis is driven, solvent is dimethyl sulfoxide (DMSO)；
(3) the rotary coating CsPbBr3 precursor solutions on hole transmission layer；
(4) annealed in heating plate, evaporation solvent obtains CsPbBr3 film photosensitive layers, and described annealing temperature is 90-200 DEG C, is moved back
Fiery time 10-30 minutes.
Further, a kind of manufacture method of the CsPbBr3 photovoltaic cells of described phthalocyanine dye sensitization, its feature exists
In described synthesis CsPbBr3 polycrystalline methods are to include step：
(1) 3.65 g PbBr2 is taken, is dissolved among the HBr solution that 15ml mass fraction is 48%, obtains solution A；
(2) 2.13 g CsBr is taken, solution obtains B solution in 5ml deionized water；
(3) solution A is sufficiently mixed with B solution, obtains crocus solute；
(4) it is dried in vacuo after gained crocus solute is washed with absolute ethyl alcohol, obtains CsPbBr3 polycrystalline.
Further, the manufacture method of the CsPbBr3 photovoltaic cells of described a kind of phthalocyanine dye sensitization, it is characterised in that
Dye-sensitized layer is formed on CsPbBr3 film photosensitive layers includes step：
(1) substrate for completing CsPbBr3 film photosensitive layers is loaded into ultrahigh vacuum coating system, and is loaded into required phthalocyanine dye
Expect material；
(2) ultrahigh vacuum coating system is evacuated to vacuum less than 5 × 10-4Pa；
(3) phthalocyanine dye is deposited on CsPbBr3 film photosensitive layers using the method for vacuum thermal evaporation.
Compared with prior art, the beneficial effects of the invention are as follows：(1) lacking for CsPbBr3 thin film surface planenesses is improved
Fall into, phthalocyanine dye layer can fill the hole of CsPbBr3 film surfaces, it is to avoid electron transfer layer and the direct of hole transmission layer connect
Touch, reduce the recombination probability of electron hole, increase the parallel resistance of battery, improve the short circuit current flow of battery, fill factor, curve factor and open
Road voltage and the energy conversion efficiency for finally improving battery.(2) the photoresponse scope of battery is increased；Because phthalocyanine dye layer is can
See that optical range possesses good light absorbs, it, which absorbs the light-generated excitons produced after light, to occur with the interface of electron transfer layer
Decompose, form photogenerated current, so the introducing of phthalocyanine dye layer can strengthen the absorption of battery, and finally improve the energy of battery
Conversion efficiency.(3) life-span of battery is improved；Due to phthalocyanine dye under the conditions of air and most chemical solvents chemical property
Temperature, can play a good protection to battery CsPbBr3 film layers, improve the life-span of battery.
Brief description of the drawings
The CsPbBr3 photovoltaic cells that Fig. 1 is sensitized for the phthalocyanine dye of the present invention；
Fig. 2 is CsPbBr3 film photosensitive layer surface topography maps of the invention；
Fig. 3 is the absorption spectrum of the CsPbBr3 film photosensitive layers of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiments.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
Referring to Fig. 1, the present invention provides a kind of technical scheme：
A kind of CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization, it is characterised in that including electrically conducting transparent substrate, hole transmission layer,
CsPbBr3 films photosensitive layer, dye-sensitized layer, electron transfer layer, electrode modification layer and reflecting electrode are constituted；
Further, described CsPbBr3 films photosensitive layer is CsPbBr3 polycrystalline, is formed on hole transmission layer,
The surface Root Mean Square roughness of CsPbBr3 film photosensitive layer thickness 100-300 nm, CsPbBr3 film photosensitive layers is 20-40
nm；
Further, described dye-sensitized layer be phthalocyanine dye, dye-sensitized layer formation CsPbBr3 films photosensitive layer it
On, described dye-sensitized layer is preferably SubPc, ClAlPc, SubNc, thickness 10-20 nm.
Further, described electrically conducting transparent substrate is made a living the quartz glass with ITO, silicate glass, high silica glass
The clear glass such as glass or soda-lime glass, the ITO thickness is preferably 100-300 nm, and light transmittance is more than 85%, and square resistance is small
In 10 Ω.
Described hole transmission layer formation is on electrically conducting transparent substrate, and described hole transmission layer includes but is not limited to stone
Black alkene, PEDOT:PSS, PTAA, polyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE, PEI, it is empty
Cave transport layer thickness is preferably 10-50 nm.
Further, described electron transfer layer formation is on dye-sensitized layer, described electron transfer layer include but
C60, C70, PCBM are not limited to, electron transfer layer thickness is preferably 20-50 nm.
Further, described electrode modification layer is formed on electron transfer layer, described electrode modification layer is BCP,
One kind in Bphen, Alq3, TPBI, preferred thickness is 5-10 nm.
Further, the formation of described reflecting electrode is on electrode modification layer, and described reflecting electrode includes but do not limited
In Al, Au, Ag, the preferred thickness 100-1000 nm of reflecting electrode.
A kind of manufacture method of the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization, it is characterised in that the preparation of device is by first
Order includes step successively afterwards：
(1) electrically conducting transparent substrate is cleaned；
(2) hole transmission layer is formed in electrically conducting transparent substrate；
(3) CsPbBr3 film photosensitive layers are formed on hole transmission layer；Including step：
A, synthesis CsPbBr3 polycrystalline；3.65 g PbBr2 is taken, is dissolved among the HBr solution that 15ml mass fraction is 48%,
Obtain solution A；2.13 g CsBr is taken, solution obtains B solution in 5ml deionized water；Solution A is abundant with B solution
Mixing, obtains crocus solute；It is dried in vacuo after gained crocus solute is washed with absolute ethyl alcohol, obtains CsPbBr3 polycrystalline；
B, configuration CsPbBr3 precursor solutions, before the concentration of the CsPbBr3 precursor solutions is 0.5 M, the CsPbBr3
CsPbBr3 polycrystalline of the solute of liquid solution for synthesis is driven, solvent is dimethyl sulfoxide (DMSO)；
C, the rotary coating CsPbBr3 precursor solutions on hole transmission layer；
Annealed on D, heating plate, evaporation solvent obtains CsPbBr3 film photosensitive layers, described annealing temperature is 90-200 DEG C；
(4) dye-sensitized layer is formed on CsPbBr3 film photosensitive layers；Including step：
A, the substrate loading ultrahigh vacuum coating system that CsPbBr3 film photosensitive layers will be completed, and it is loaded into required phthalocyanine dye
Expect material；
B, ultrahigh vacuum coating system is evacuated to vacuum less than 5 × 10-4Pa；
C, using the method for vacuum thermal evaporation phthalocyanine dye is deposited on CsPbBr3 film photosensitive layers；
(5) electron transfer layer is formed on dye-sensitized layer；
(6) electrode modification layer is formed on the electron transport layer；
(7) reflecting electrode is formed in electrode transport layer.
Embodiment one
The CsPbBr3 photovoltaic cells and its manufacture method of a kind of phthalocyanine dye sensitization, it is from the bottom to top Glass/ that device architecture, which is,
ITO/ PEDOT:PSS/ CsPbBr3/SubPc/C60/Bphen/Al。
An ito glass substrate is provided, ITO thickness is preferably 100-300 nm, and light transmittance is more than 85%, and square resistance is less than
10 Ω, make CsPbBr3 photovoltaic cells as steps described below：
(1) electrically conducting transparent substrate is cleaned：Electrically conducting transparent substrate is cleaned by ultrasonic 20 points successively using acetone, isopropanol, deionized water
Clock, ultra violet lamp is used 20 minutes after nitrogen drying；
(2) hole transmission layer is formed in electrically conducting transparent substrate：Take PEDOT:PSS is as hole transmission layer, using rotary coating
Method be deposited on transparent conductive substrates, rotating speed 4000 rpm, time 40s, afterwards in 120 DEG C of heating plates anneal
Processing 30 minutes；
(3) CsPbBr3 film photosensitive layers are formed on hole transmission layer, CsPbBr3 films photosensitive layer is prepared according to following steps
It is rapid to carry out：
A, synthesis CsPbBr3 polycrystalline；3.65 g PbBr2 is taken, is dissolved among the HBr solution that 15ml mass fraction is 48%,
Obtain solution A；2.13 g CsBr is taken, solution obtains B solution in 5ml deionized water；Solution A is abundant with B solution
Mixing, obtains crocus solute；It is dried in vacuo after gained crocus solute is washed with absolute ethyl alcohol, obtains CsPbBr3 polycrystalline；
B, configuration CsPbBr3 precursor solutions, before the concentration of the CsPbBr3 precursor solutions is 0.5 M, the CsPbBr3
CsPbBr3 polycrystalline of the solute of liquid solution for synthesis is driven, solvent is dimethyl sulfoxide (DMSO)；
C, the rotary coating CsPbBr3 precursor solutions on hole transmission layer：The rpms of rotary coating rotating speed 2000, the time is 30
s；
Annealed on D, heating plate：Evaporation solvent obtains CsPbBr3 film photosensitive layers, and described annealing temperature is 90 DEG C, during annealing
Between be 30 minutes；
(4) dye-sensitized layer is formed on CsPbBr3 film photosensitive layers, dye-sensitized layer is prepared and carried out as steps described below：
A, the substrate loading ultrahigh vacuum coating system that CsPbBr3 film photosensitive layers will be completed, and it is loaded into required phthalocyanine dye
Expect material SubPc；
B, ultrahigh vacuum coating system is evacuated to vacuum less than 5 × 10-4Pa；
C, using the method for vacuum thermal evaporation phthalocyanine dye is deposited on CsPbBr3 film photosensitive layers, sedimentation rate is
0.02 nm/s, sedimentation rate is monitored by quartz crystal, and deposit thickness is 10 nm；
(5) electron transfer layer is formed on dye-sensitized layer：The C60 for growing one layer of 40 nm by the method for hot evaporation is used as electricity
Sub- transport layer；
(6) electrode modification layer is formed on the electron transport layer：One layer of 5 nm Bphen electrodes are grown by the method for hot evaporation
Decorative layer；
(7) reflecting electrode is formed in electrode transport layer：One layer of 100 nm is grown by hot evaporation or the method for magnetron sputtering
Al be used as reflecting electrode.
Referring to Fig. 2, CsPbBr3 thin film surface planenesses have larger defect, its surface has substantial amounts of hole
Hole, the presence of these holes can cause the electron transfer layers such as C60 to be contacted with the direct of hole transmission layer, increase answering for electron hole
Probability is closed, the parallel resistance of battery is reduced, causes the complete of the characterisitic parameters such as short circuit current flow, fill factor, curve factor and the open-circuit voltage of battery
Face declines, so as to reduce the efficiency of battery.The phthalocyanine dyes such as SubPc layer can fill the hole of CsPbBr3 film surfaces, it is to avoid
Electron transfer layer is directly contacted with hole transmission layer, is reduced the recombination probability of electron hole, is increased the parallel resistance of battery, carry
Short circuit current flow, fill factor, curve factor and the open-circuit voltage of high battery and the energy conversion efficiency for finally improving battery.
Referring to Fig. 3, CsPbBr3 light abstraction width is within the scope of 300-520 nm, in the visible of 520-760 nm
Optical range and near infrared region absorb weaker or not absorbed, and which greatly limits the photoelectric current of CsPbBr3 batteries and battery
Efficiency.Because phthalocyanine dye layer possesses good light absorbs in visible-range, it absorbs after light the light-generated excitons that produce can be with
Decomposed at the interface with electron transfer layer, form photogenerated current, so the introducing of phthalocyanine dye layer can strengthen battery
Absorb, and finally improve the energy conversion efficiency of battery.10 nm SubPc phthalocyanine dyes are introduced as the photosensitive layer of battery,
Because SubPc in 520-600 nm has preferable absorption, it can greatly strengthen battery from 520 nm to 600 nm optical responsivities,
So as to improve the efficiency of battery.
In addition CsPbBr3 batteries also have CsPbBr3 to water sensitive, the problem of influenceing its life-span.Due to phthaleins such as SubPc
Cyanine dyes chemical property temperature under the conditions of air and exhausted big how many chemical solvent, can be played to battery CsPbBr3 film layers
Good protective effect, improves the life-span of battery.
By contrast test, the CsPbBr3 photovoltaics that the present invention is sensitized using SubPc as the phthalocyanine dye of dye-sensitized layer
The short-circuit current density of battery is 4.3 mA/cm2, the V of open-circuit voltage 1.32, fill factor, curve factor 0.45, energy conversion efficiency is
2.55%, the CsPbBr3 photovoltaic cells comparative example without dye-sensitized layer is 2.3 compared to the short-circuit current density of photovoltaic cell
MA/cm2, the V of open-circuit voltage 1.12, fill factor, curve factor 0.34, energy conversion efficiency is 0.87%, what phthalocyanine dye of the invention was sensitized
CsPbBr3 photovoltaic cells energy conversion efficiency is improved more than 100%.Significantly increase in addition, the life-span of battery also has.Setting electricity
Pond energy conversion efficiency drop to the 50% of starting efficiency as battery life-span, the CsPbBr3 of phthalocyanine dye sensitization of the invention
Photovoltaic cell energy conversion life-span compared with comparative device improves more than 3 times.
Embodiment two
The CsPbBr3 photovoltaic cells and its manufacture method of a kind of phthalocyanine dye sensitization, it is from the bottom to top Glass/ that device architecture, which is,
ITO/ PEDOT:PSS/ CsPbBr3/ClAlPc/PCBM/BCP/Ag。
Any of the above-described ito glass substrate is provided, ITO thickness is preferably 100-300 nm, and light transmittance is more than 85%, square electricity
Resistance is less than 10 Ω, and CsPbBr3 photovoltaic cells are made as steps described below：
(1) electrically conducting transparent substrate is cleaned：Be the same as Example one；
(2) hole transmission layer is formed in electrically conducting transparent substrate：Be the same as Example one；
(3) CsPbBr3 film photosensitive layers are formed on hole transmission layer, CsPbBr3 films photosensitive layer is prepared according to following steps
It is rapid to carry out：
A, synthesis CsPbBr3 polycrystalline:Be the same as Example one；
B, configuration CsPbBr3 precursor solutions:Be the same as Example one；
C, the rotary coating CsPbBr3 precursor solutions on hole transmission layer：The rpms of rotary coating rotating speed 4000, the time is 50
s；
Annealed on D, heating plate：Evaporation solvent obtains CsPbBr3 film photosensitive layers, and described annealing temperature is 200 DEG C, during annealing
Between be 10 minutes；
(4) dye-sensitized layer is formed on CsPbBr3 film photosensitive layers, dye-sensitized layer is prepared and carried out as steps described below：
A, the substrate loading ultrahigh vacuum coating system that CsPbBr3 film photosensitive layers will be completed, and it is loaded into required phthalocyanine dye
Expect material C lAlPc；
B, ultrahigh vacuum coating system is evacuated to vacuum less than 5 × 10-4Pa；
C, using the method for vacuum thermal evaporation phthalocyanine dye is deposited on CsPbBr3 film photosensitive layers, sedimentation rate is
0.05 nm/s, sedimentation rate is monitored by quartz crystal, and deposit thickness is 20 nm；
(5) electron transfer layer is formed on dye-sensitized layer：One layer PCBM layers, which are grown, by the method for rotary coating is used as electronics
Transport layer；
(6) electrode modification layer is formed on the electron transport layer：One layer of 10 nm BCP electrodes are grown by the method for hot evaporation
Decorative layer；
(7) reflecting electrode is formed in electrode transport layer：One layer of 200 nm is grown by hot evaporation or the method for magnetron sputtering
Ag be used as reflecting electrode.
Described in beneficial effect be the same as Example one, specifically：(1) ClAlPc phthalocyanine dyes sensitizing layer can be filled
The hole of CsPbBr3 film surfaces；(2) ClAlPc phthalocyanine dyes sensitizing layer can strengthen battery in 520-900 nm scopes
Absorb, so as to improve battery efficiency；(3) ClAlPc phthalocyanine dyes sensitizing layer can protect CsPbBr3 films, improve battery
Life-span.Test result shows that the efficiency of battery and life-span are enhanced about more than once.
It following is a brief introduction of work and the realization principle of the present invention.Present invention introduces the raising of phthalocyanine dye sensitizing layer
It is based on the reason for following several respects that the efficiency of CsPbBr3 photovoltaic cells and life-span, which succeed,：(1) perovskite material exciton
With reference to energy very little, have been reported that its exciton binding energy is less than 0.1 eV, so the light-generated excitons formed in CsPbBr3 perovskites are very
Free electron and hole can be voluntarily dissociated into big degree, without being diffused into its interface with electron transfer layer, even if drawing
Phthalocyanine dye sensitizing layer is entered, the formation of exciton dissociation and photoelectric current in CsPbBr3 photosensitive layers is not hindered；(2) phthalocyanine contaminates
Material class material possesses the light induced electron formed in good bipolar transmission performance, i.e. CsPbBr3 photosensitive layers can be by sensitization
Layer is transferred to electron transfer layer and finally collected by electrode, and dye-sensitized layer is introduced into the biography for not having an impact electric charge in prototype part
Defeated and collection.(3) CsPbBr3 films photosensitive layer surface roughness is big, there is more hole.Even if introducing certain thickness
Sensitizing layer, such as 20 nm, the CsPbBr3 layers of contact with electron transfer layer, or CsPbBr3 layers and electricity can not be completely cut off completely
The actual range of sub- transport layer is less than the thickness of sensitizing layer, this also increases exciton in CsPbBr3 in itself and electric transmission stratum boundary
The possibility that face is decomposed, while shortening electric transmission distance, is conducive to the collection of light induced electron formed in CsPbBr3.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization, it is characterised in that including electrically conducting transparent substrate, hole transport
Layer, CsPbBr3 films photosensitive layer, dye-sensitized layer, electron transfer layer, electrode modification layer and reflecting electrode are constituted；Described
Dye-sensitized layer is phthalocyanine dye, and dye-sensitized layer is preferably one kind in SubPc, ClAlPc, SubNc, and described dyestuff is quick
Change layer formation on CsPbBr3 film photosensitive layers, thickness 10-20 nm.
2. a kind of CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization, it is characterised in that described CsPbBr3 film photosensitive layers are
CsPbBr3 polycrystalline, is formed on hole transmission layer；Described CsPbBr3 film photosensitive layer thickness 100-300 nm,
The surface Root Mean Square roughness of CsPbBr3 film photosensitive layers is 20-40 nm.
3. the CsPbBr3 photovoltaic cells of a kind of phthalocyanine dye sensitization as claimed in claim 1, it is characterised in that described is saturating
Bright conductive substrates are made a living the clear glasses such as the quartz glass with ITO, silicate glass, vagcor or soda-lime glass, institute
It is preferably 100-300 nm to state ITO thickness, and light transmittance is more than 85%, and square resistance is less than 10 Ω.
4. the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization as claimed in claim 1, it is characterised in that described hole is passed
Defeated layer formation is on electrically conducting transparent substrate；Described hole transmission layer includes but is not limited to graphene, PEDOT:PSS、PTAA、
PolyTPD, CuSCN, CuI, MoOx, V2O5, NiO, spiro-OMeTAD, PEIE, PEI, thickness of hole transport layer are preferably 10-
50 nm。
5. the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization as claimed in claim 1, it is characterised in that described electronics is passed
Defeated layer formation is on dye-sensitized layer；Described electron transfer layer includes but is not limited to C60, C70, PCBM, electron transfer layer
Thickness is preferably 20-50 nm.
6. the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization as claimed in claim 1, it is characterised in that described electrode is repaiied
It is one kind in BCP, Bphen, Alq3, TPBI to adorn layer, and electrode modification layer preferred thickness is 5-10 nm.
7. the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization as claimed in claim 1, it is characterised in that described reflection electricity
Pole is formed on electrode modification layer；Described reflecting electrode includes but is not limited to Al, Au, Ag, the preferred thickness of reflecting electrode
100-1000 nm。
8. a kind of manufacture method of the CsPbBr3 photovoltaic cells of phthalocyanine dye sensitization as claimed in claim 1, its feature exists
In the preparation of device sequentially includes step successively：
(1) electrically conducting transparent substrate is cleaned；
(2) hole transmission layer is formed in electrically conducting transparent substrate；
(3) CsPbBr3 film photosensitive layers are formed on hole transmission layer；
(4) dye-sensitized layer is formed on CsPbBr3 film photosensitive layers；
(5) electron transfer layer is formed on dye-sensitized layer；
(6) electrode modification layer is formed on the electron transport layer；
(7) reflecting electrode is formed on electrode modification layer.
9. claim 1 or claim 8 it is any as described in a kind of phthalocyanine dye be sensitized CsPbBr3 photovoltaic cells manufacture
Method, it is characterised in that forming CsPbBr3 films photosensitive layer includes step：
(1) CsPbBr3 polycrystalline is synthesized：Take 3.65 g PbBr2, be dissolved in 15ml mass fraction for 48% HBr solution it
In, obtain solution A；2.13 g CsBr is taken, solution obtains B solution in 5ml deionized water；Solution A is filled with B solution
Divide mixing, obtain crocus solute；It is dried in vacuo after gained crocus solute is washed with absolute ethyl alcohol, obtains CsPbBr3 many
It is brilliant；
(2) CsPbBr3 precursor solutions are configured, before the concentration of the CsPbBr3 precursor solutions is 0.5 M, the CsPbBr3
CsPbBr3 polycrystalline of the solute of liquid solution for synthesis is driven, solvent is dimethyl sulfoxide (DMSO)；
(3) the rotary coating CsPbBr3 precursor solutions on hole transmission layer；
(4) made annealing treatment in heating plate, evaporation solvent obtains CsPbBr3 film photosensitive layers, described annealing temperature is 90-200
DEG C, annealing time is 10-30 minutes.
10. claim 1 or claim 8 it is any as described in phthalocyanine dye be sensitized CsPbBr3 photovoltaic cells manufacturer
Method, it is characterised in that forming dye-sensitized layer includes step：
(1) substrate for completing CsPbBr3 film photosensitive layers is loaded into ultrahigh vacuum coating system, and is loaded into required phthalocyanine dye
Expect material；
(2) ultrahigh vacuum coating system is evacuated to vacuum less than 5 × 10-4Pa；
(3) phthalocyanine dye is deposited on CsPbBr3 film photosensitive layers using the method for vacuum thermal evaporation.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108258126A (en) * | 2018-01-29 | 2018-07-06 | 芜湖乐知智能科技有限公司 | A kind of photodetector based on inorganic perovskite and preparation method thereof |
| CN109516496A (en) * | 2018-12-18 | 2019-03-26 | 江南大学 | A kind of full-inorganic perovskite CsPbBr of stable dispersion3Nanocrystalline preparation method |
| CN110323068A (en) * | 2018-03-30 | 2019-10-11 | 株式会社理光 | Photo-electric conversion element, photoelectric conversion device module, electronic device and power module |
| CN114864829A (en) * | 2022-07-07 | 2022-08-05 | 中国长江三峡集团有限公司 | Perovskite solar cell and preparation method thereof |
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| WO2015189551A1 (en) * | 2014-06-12 | 2015-12-17 | Isis Innovation Limited | Heterojunction device |
| CN105514282A (en) * | 2016-02-05 | 2016-04-20 | 南方科技大学 | Solar cell and method for producing a solar cell |
| CN105742508A (en) * | 2016-04-12 | 2016-07-06 | 上海大学 | Preparation method for perovskite solar cell with tetramino zinc phthalocyanine organic hole transmission layer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015189551A1 (en) * | 2014-06-12 | 2015-12-17 | Isis Innovation Limited | Heterojunction device |
| CN105514282A (en) * | 2016-02-05 | 2016-04-20 | 南方科技大学 | Solar cell and method for producing a solar cell |
| CN105742508A (en) * | 2016-04-12 | 2016-07-06 | 上海大学 | Preparation method for perovskite solar cell with tetramino zinc phthalocyanine organic hole transmission layer |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108258126A (en) * | 2018-01-29 | 2018-07-06 | 芜湖乐知智能科技有限公司 | A kind of photodetector based on inorganic perovskite and preparation method thereof |
| CN108258126B (en) * | 2018-01-29 | 2019-07-16 | 芜湖乐知智能科技有限公司 | A kind of photodetector and preparation method thereof based on inorganic perovskite |
| CN110323068A (en) * | 2018-03-30 | 2019-10-11 | 株式会社理光 | Photo-electric conversion element, photoelectric conversion device module, electronic device and power module |
| CN110323068B (en) * | 2018-03-30 | 2021-12-07 | 株式会社理光 | Photoelectric conversion element, photoelectric conversion element module, electronic device, and power supply module |
| CN109516496A (en) * | 2018-12-18 | 2019-03-26 | 江南大学 | A kind of full-inorganic perovskite CsPbBr of stable dispersion3Nanocrystalline preparation method |
| CN109516496B (en) * | 2018-12-18 | 2020-11-03 | 江南大学 | Stably dispersed all-inorganic perovskite CsPbBr3Method for preparing nanocrystalline |
| CN114864829A (en) * | 2022-07-07 | 2022-08-05 | 中国长江三峡集团有限公司 | Perovskite solar cell and preparation method thereof |
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