CN105655491B - The organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity - Google Patents
The organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity Download PDFInfo
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- CN105655491B CN105655491B CN201610183854.7A CN201610183854A CN105655491B CN 105655491 B CN105655491 B CN 105655491B CN 201610183854 A CN201610183854 A CN 201610183854A CN 105655491 B CN105655491 B CN 105655491B
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- H—ELECTRICITY
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
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Abstract
The invention discloses a kind of organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity, this device includes substrate, transparent electrode, hole injection layer, exciton barrier-layer, donor layer, receptive layers, electron transfer layer and electrode cathode.It is exciton barrier-layer in place of the feature of the device, by match materials, this exciton barrier-layer had both been able to achieve electronics in effective blocking of anode tap, reduced the dark current component and electron leakage current of photovoltaic cell；Sunlight middle-ultraviolet lamp transmitting ethereal blue or day blue light can be absorbed again, enhance the incident photon quantity of subsequent organic solar batteries active layer.Photogenerated current is improved to improve the power conversion efficiency of photovoltaic cell.Device disclosed by the invention realizes the double effects of exciton blocking and sunlight enhancing with a kind of simple method in the case where designing without other extra opticals and complicated technology simultaneously.Preparation process is simple, equipment requirement is low, is suitble to volume production.
Description
Technical field
The present invention relates to a kind of organic optoelectronic devices and preparation method thereof, more particularly to a kind of organic solar batteries
(OPV) and preparation method thereof, it is applied to green solar source technology field.
Background technique
Organic optoelectronic technology is that academia of the world develops swift and violent one of high-tech in the past 10 years.With film technique
The diversity of fast-developing and organic material or organic/inorganic hybridization material design, organic electroluminescence device, organic solar
The organic optoelectronics products such as battery (organic photovoltaic cell, OPV), organic field effect tube gradually develop
Maturation, and have many advantages, such as to be easy to large area preparation, flexible, shock pressure.Wherein, the organic solar batteries of clean energy resource are utilized
The advantages that environmentally protective by its, inexpensive, attracts tremendous attention in energy technology field；Using small organic molecule/polymer material
And easy film-forming process has been achieved for the breakthrough that photoelectric conversion efficiency is more than 12%, to alleviate the withered of fossil energy
It exhausts and guarantees that the sustainable development of human society provides good solution.Planar heterojunction in especially OPV due to
Its structure is simple, of less demanding to material purity, therefore is researcher desk study material property and device architecture performance
First choice.
However, traditional OPV device has the shortcomings that:
1. the ratio of ultraviolet light in solar spectrum, visible light, infrared light is fixed, if you need to enhance light intensity of certain a part, need
By physical optics design or prepare the micro-nano structure of Special complex with achieve the purpose that optically focused or enhancing reflection and refraction or
The absorption to sunlight is widened by the tandem type OPV (cascade OPV) of design complex configurations；
2. the exciton dissociation to/receptor in traditional planar heterojunction battery is not enough, cause short circuit current inclined
It is low；
3. appearance structure is complicated in bulk heterojunction, it is more difficult to accurately control, the unknown place of mechanism is more；
4. the injection of hole and electronics and transmission rate mismatch cause the photogenerated current finally generated limited.
The injection of traditional hole or transmission material are poly (3,4-ethylenedioxythiophene): poly in OPV
(styrenesulfonate) (PEDOT:PSS) has excellent smooth electrically-conductive backing plate, leakage current is inhibited to obtain higher open circuit
The effect of voltage, however be also simultaneously strong Exciton quenching agent, this affects OPV in the popularization in practical application field.
Summary of the invention
In order to solve prior art problem, it is an object of the present invention to overcome the deficiencies of the prior art, and to provide one kind
The organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity, using increasing
Add anode tap exciton barrier-layer, forms transparent anode-hole injection layer-exciton barrier-layer-donor layer NEW TYPE OF COMPOSITE in OPV
Functional layer structure makes integral type hole transmission layer can be achieved at the same time the effect of exciton blocking and sunlight enhanced sensitivity, work of the present invention
Skill is simple, while saving material, reduces cost, has great industrial value.
Purpose is created to reach foregoing invention, insight of the invention is that
It creates based on the organic solar batteries device with exciton blocking and the integral type hole transmission layer of sunlight enhanced sensitivity
Part, device are mainly characterized by not needing additional complicated optical design or prepare micro-nano structure to enhance sunlight intensity or mention
For advantageous reflection and refraction, the i.e. absorbable ultraviolet light emission blue light of this hole transmission layer or green light are to additionally increase incident light
Photon numbers, and there is electronic blocking effect simultaneously.Device architecture is simple, and single hole transmission layer is provided simultaneously with two kinds of functions,
And its energy level is matched with donor layer and is had no adverse effects to device open-circuit voltage, higher hole mobility will not constraint device filling
The factor.By reasonably selecting material, exciton blocking and sunlight sensitization are dexterously realized simultaneously.
Conceived according to foregoing invention, adopted the following technical solutions:
A kind of organic solar batteries of the integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity, from it is lower to
On successively by substrate layer, transparent conductive anode layer, hole injection layer, exciton barrier-layer, donor layer, receptive layers, electron transfer layer
It combines and forms with electrode cathode layer, donor layer has any one in the organic solar battery material absorbed by force using narrowband system
Material or any different materials are made, and receptive layers are using fullerene or any one material in fullerene derivate material or appoint
Meaning different materials be made, exciton barrier-layer with a thickness of 5-20nm, the material of exciton barrier-layer is the tool UV absorption of broad-band gap
And the hole mobile material of visible light is hardly picked up, and the level-density parameter of the energy level of exciton barrier-layer and donor layer.
Substrate composed by above-mentioned transparent substrates and transparent conductive anode with a thickness of 100-150nm, above-mentioned hole injection
The thickness of layer is preferably 5-10nm, and the thickness of above-mentioned donor layer is preferably 10-25nm, and the thickness of above-mentioned receptive layers is preferably 30-
50nm, the thickness of above-mentioned electron transfer layer are preferably 5-10nm, and the thickness of above-mentioned electrode cathode layer is preferably 80-100nm.
Above-mentioned exciton blocking layer material preferably uses blue fluorescent material, green fluorescent material, blue phosphor materials and green
Any one material or any different materials in color phosphor material, blue fluorescent material use dark blue dyestuff 5- (4- (4,6-
diphenyl-1,3,5-triazin-2-yl)phenyl)-10,10-diphenyl-5,10-dihydrodibenzo[b,e]
[1,4]azasiline (DTPDDA)、4,4’-Bis(2,2-diphenylvinyl)-1,1’-biphenyl(DPVBi)、
diphenyl-(4-{2-[4-(2-pyridin-4-yl-vinyl)-phenyl]-vinyl}-phenyl)-amine(DPVPA)、
2,7-bis[2-(4-tert-butylphenyl) pyrimidine-5-yl]-9,9’-spirobifluorene(TBPSF)、
5,10,15-tribenzyl-5H-diindolo [3,2-a:3’,2’-c]-carbazole(TBDI)、N,N’-diphenyl-
N, N’-bis(1-naphthyl phenyl)-1,1’-biphenyl-4,4’-diamine (α-NPD)、N,N’-diphenyl
-N,N’-bis(1-naphthyl)-1,1’-bipheny l-4,4’-diamine(NPB)、 4,4’-bis-9-carbozyl
biphenyl (CBP)、4,4’-bis[(N-carbazole) styryl]biphenyl (BSB-Cz)、2,4-bis{3-(9H
- carbazol-9-yl) -9H-carbazol-9-yl } it is any one in -6-phen yl-1,3,5-triazine (CC2TA)
Kind material or any different materials；Green fluorescent material uses rhodamine 6G (R6G), 2,3,6,7-tetra hydro-
1,1,7,7- tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinoli zino-[9,9a,1gh]
coumarin (C545 T)、(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophth alonitrile
Any one material or any different materials in (4CzIPN)；Blue phosphor materials use iridium bis (4,6-
difloroPhenyl-pyridi nato-N,C’)picolinate (Firpic)、iridium (Ⅲ)bis(4,6-
difluorophenylpyridinato)tetra kis(1-pyraZolyl)borate (Fir6)、Iridium(Ⅲ)bis
(4,6-difluorophenyl-pyridinato) -5- (pyridine-2-yl) -1H-tetrazolate) in (FirN4)
Any one material or any different materials；Green phosphorescent material uses fac-tris (2-phenylpyridine)
iridium (Ir(ppy)3)、bis(2-phenyl pyridine) iridium(acetyl-acetonate) ((ppy)2Ir
And tris [3,6-bis (phenyl)-pyridazinato-N (acac))1, C2’]iridium (Ir(BPP ya)3) in
Any one material or any different materials.
The material of above-mentioned substrate layer is preferably nonbreakable glass material, transparent polymer flexible material or biodegradable soft
Property material in any one material or any several composite material, wherein transparent polymer flexible material be polyethylene, it is poly-
Any one in methyl methacrylate, polycarbonate, polyurethanes, polyimides, polyamides resin and polyacrylic acid
Material or any different materials.
The material of above-mentioned transparent conductive anode is preferably tin indium oxide (ITO), conducting polymer poly (3,4-
Ethylenedioxy thiophene): poly (styrenesulfonate) (PEDOT:PSS), graphene (graphene),
Carbon nanotube (carbon nanotube), metal simple-substance, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction are received
Any one material or any different materials in rice noodles.
The material of above-mentioned hole injection layer is preferably MoO3、V2O5、NiO2、WO3In any one material or any several
Material.
The material of above-mentioned donor layer is preferably the boron subphthalocyanine in narrowband system donor material
chloride (SubPc)、copper phthalocyanine (CuPc)、chloroaluminium phthalocyanine
(ClAlPc)、zinc phthalocyanine (ZnPc)、rubrene、tetraphenyldibenzoperiflanthene
(DBP)、bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2’]iridium(acetylacetonate)
(t-bt)2Ir (acac)、4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-
Tetramethyljulolidyl-9- enyl) any one material or any several materials in -4H-pyran (DCJTB)
Material.
Above-mentioned receptor layer material is preferably the C in fullerene or fullerene derivate material60、C70、[6,6]-phenyl
C71 butyric acid methyl ester (PC71BM)、[6,6]-phenyl C61 butyric acid methyl
ester (PC61BM)、indene-C60 bisadduct (ICBA)、poly(9,9-dioctylfluorene-co-
Any one material or any different materials in benzothiadiazole (F8BT).
The material of above-mentioned electron transfer layer is preferably graphene, carbon nanotube, ZnO, Cs2CO3、2,2', 2”-(1,3,5-
benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi)、bathocuproine (BCP)、
Lithium Fluoride (LiF), tris- (8-hydroxyquinolinato) aluminum (Alq3), other oxadiazoles
Class compound, quinoxaline compound, the polymer of cyano-containing, other nitrogen-containing heterocycle compounds, organosilicon material, perfluorinated material
Any one material or any different materials in material and organic boron material.
Above-mentioned electrode cathode layer is preferably any one material or any several in Al, Ag, magnesium silver alloy and lithium-aluminium alloy
Kind material.
A kind of organic solar batteries of integral type hole transmission layer of the present invention with exciton blocking and sunlight enhanced sensitivity
Preparation method, which comprises the following steps:
1) substrate composed by transparent substrates and transparent conductive anode is cleaned, is dried up after cleaning with drying nitrogen;
2) using rotary coating, printing, spraying or vapor deposition mode, and hole injection layer material is used, in step 1)
Transparent conductive anode prepares hole injection layer on surface；
3) using rotary coating, printing, spraying or vapor deposition mode, and hole mobile material is used, the preparation in step 2)
Hole injection layer surface on prepare exciton barrier-layer again；
4) using rotary coating, printing, spraying or vapor deposition mode, and organic electronic donor layer material is used, in step 3)
Donor layer is prepared again in the exciton blocking layer surface of middle preparation；
5) using rotary coating, printing, spraying or vapor deposition mode, and electron acceptor layer material is used, the system in step 4)
Receptive layers are prepared again in standby donor layer surface；
6) using rotary coating, printing, spraying or vapor deposition mode, and electron transport layer materials are used, the system in step 5)
Electron transfer layer is prepared again in standby receptor layer surface；
7) it is masked plate replacement, evaporation cathode material, formation are electric again for the electron-transport layer surface prepared in step 6)
Pole cathode layer, so that each functional layer of organic solar batteries be made.
The present invention is based on the organic solar batteries with exciton blocking and the integral type hole transmission layer of sunlight enhanced sensitivity
The preparation method of device is to be hindered in the transparent electrode of device by being sequentially depositing hole injection layer, hole transmission layer i.e. exciton
Barrier is sequentially depositing donor layer, receptive layers and electronics by vacuum evaporation, spin coating or print process then on exciton barrier-layer
Transport layer finally passes through vacuum vapour deposition depositing electrode cathode on the electron transport layer.The present invention is in hole injection layer and donor
The exciton barrier-layer that a broad-band gap is inserted between material can effectively prevent Exciton quenching, reduce the dark current component of photovoltaic cell
And electron leakage current.In addition the addition of exciton barrier-layer is conducive to balance the transmission performance in hole and electronics, makes electron hole
More it is limited in active layer to be separated, to enhance photoelectric current.Additionally by reasonably select material, it is deposited on sunlight and enters
The exciton barrier-layer for penetrating end can absorb ultraviolet light and generate the visible light that can be absorbed to/acceptor material to increase consequent activities
The incident photon quantity of layer, this is a kind of simple and effective enhanced sensitivity sunlight thus the method for improving photogenerated current.
The present invention compared with prior art, has following obvious prominent substantive distinguishing features and remarkable advantage:
1. the exciton barrier-layer in device of the present invention is same relative to traditional OPV structure with single hole injection layer
When have and stop electronics, prevent Exciton quenching, reduce dark current component and electron leakage current and transmitting blue light or green light are to increase
The effect of sunlight photon numbers is penetrated in trunk offering；
2. the present invention by reasonably select exciton blocking layer material, be allowed to energy level match with donor layer, emission spectrum and to/
The absorption spectrum of receptive layers matches, and the light absorption of itself does not influence the absorption of active layer；
3. exciton barrier-layer thickness control prepared by the present invention plays an important role to the performance of entire device, exciton resistance
The thickness optimum control of barrier is too thin too thick to reduce shorted devices electric current and fill factor in 5-20nm；
4. device architecture of the present invention is simple, exciton barrier-layer thickness and ingredient can be controlled accurately, available stable
Performance, therefore be conducive to preparation cascade OPV device or volume production.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of various embodiments of the present invention organic solar batteries.
Fig. 2 is the different exciton barrier-layer NPB of various embodiments of the present invention and the absorption coefficient characteristic curve of BSB-Cz monofilm.
Fig. 3 is the different exciton barrier-layer NPB of various embodiments of the present invention and the fluorescence spectrum of BSB-Cz monofilm normalizes spy
Linearity curve.
Fig. 4 is donor DBP, SubPc and receptor C of various embodiments of the present invention60The absorption coefficient characteristic curve of monofilm.
Specific embodiment
Details are as follows for the preferred embodiment of the present invention:
Embodiment one:
In the present embodiment, referring to Fig. 1, a kind of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity
Organic solar batteries, from top to bottom successively by substrate layer 1, transparent conductive anode layer 2, hole injection layer 3, exciton barrier-layer 4,
Donor layer 5, receptive layers 6, electron transfer layer 7 and electrode cathode layer 8 have 8 one functional layers altogether and combine composition, and donor layer 5 uses narrowband
The organic solar battery material that system's tool absorbs by force is made, and receptive layers 6 are made of fullerene, and the material of exciton barrier-layer 4 is
The tool UV absorption of broad-band gap and the hole mobile material for hardly picking up visible light, and the energy level and donor of exciton barrier-layer 4
The level-density parameter of layer 5.
In the present embodiment, using ito substrate composed by substrate layer 1 and transparent conductive anode layer 2, ito substrate thickness
For 150nm, that is, select the transparent IT0 glass substrate for being etched into a solid plate as anode, successively with lotion, acetone, go from
Sub- water, isopropanol are cleaned by ultrasonic 20 minutes, are dried with nitrogen, UV/O3Processing 15 minutes spare.By the method for vacuum evaporation,
MoO is deposited on IT0 glass substrate3The hole injection layer 3 with a thickness of 5nm is prepared, deposits NPB preparation then with a thickness of 5-10nm's
Exciton barrier-layer 4, following deposition thickness are the donor red dye DBP of 10-20nm to prepare donor layer 5, then deposition of thick
Degree is the C of 30-50nm60Prepare receptive layers 6, redeposition prepares electronics with a thickness of the electron transport layer materials Bphen of 5-10nm
Transport layer 7 replaces mask plate finally with evaporation cathode metal Al, prepares the electrode cathode layer 8 with a thickness of 80-100nm.
The Absorption and emission spectra of the exciton barrier-layer NPB of the present embodiment is shown in Fig. 2 and Fig. 3 respectively.The absorption peak of NPB is
348nm, emission peak 438nm.Donor layer DBP and receptive layers C60Absorption spectrum see Fig. 4.The blue light of NPB transmitting is just in C60
With the absorption region of DBP, sunlight intensity is additionally enhanced, and is not influenced to/absorption of the receptor to visible light itself.
The present embodiment be prepared for a kind of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity it is organic too
The feature place of positive energy battery, the device is exciton barrier-layer, and by match materials, this exciton barrier-layer is both able to achieve electronics
In effective blocking of anode tap, the dark current component and electron leakage current of photovoltaic cell are reduced；It can absorb again purple in sunlight
Outside line emits ethereal blue or day blue light, enhances subsequent organic solar batteries active layer i.e. to the incident photon quantity of/receptive layers.
Two aspects can improve photogenerated current to improve the power conversion efficiency of photovoltaic cell.The present embodiment OPV device is without other volumes
In the case where outer optical design and complicated technology, with a kind of simple method simultaneously realize exciton blocking and sunlight enhancing
Double effects.The present embodiment preparation process is simple, equipment requirement is low, is suitble to volume production.
Embodiment two:
The present embodiment is basically the same as the first embodiment, and is particular in that:
In the present embodiment, referring to Fig. 1, select the transparent IT0 glass substrate for being etched into a solid plate as anode,
IT0 thickness of glass substrate is 150nm.Successively it is cleaned by ultrasonic 20 minutes with lotion, acetone, deionized water, isopropanol, nitrogen is blown
It is dry, UV/O3Processing 15 minutes spare.By the method for vacuum evaporation, the deposition of hole implanted layer MoO on IT0 glass substrate3, thick
Degree is 10nm, then deposits exciton barrier-layer BSB-Cz, next thickness control deposits donor SubPc in 8-20nm, with a thickness of
7-20nm and receptive layers C60, with a thickness of 30-50nm, redeposited electron transport layer materials Bphen, with a thickness of 5-10nm, then more
Mask plate is changed with evaporation cathode metal, evaporation metal Al is cathode, with a thickness of 100nm.
The Absorption and emission spectra of the exciton barrier-layer BSB-Cz of the present embodiment is shown in Fig. 2 and Fig. 3 respectively.The absorption of BSB-Cz
Peak is 370nm, emission peak 478nm.Donor layer SubPc and receptive layers C60Absorption spectrum see Fig. 4.BSB-Cz emits bluish-green
Light is just in SubPc and C60Absorption region, additionally enhance sunlight intensity, while playing the role of electronic blocking.
The present embodiment also by match materials, same hole transmission layer can realize simultaneously exciton blocking and enhancing it is subsequent to/
The effect of incident intensity of receptive layers.With low cost, structure process is simple, and the features such as can prepare on flexible substrates.
It can be widely applied in terms of solar power generation.
The embodiment of the present invention is illustrated above in conjunction with attached drawing, but the present invention is not limited to the above embodiments, it can be with
The purpose of innovation and creation according to the present invention makes a variety of variations, under the Spirit Essence and principle of all technical solutions according to the present invention
Change, modification, substitution, combination or the simplification made, should be equivalent substitute mode, as long as meeting goal of the invention of the invention,
Without departing from the present invention have the integral type hole transmission layer of exciton blocking and sunlight enhanced sensitivity organic solar batteries and
The technical principle and inventive concept of preparation method, belong to protection scope of the present invention.
Claims (9)
1. a kind of organic solar batteries of the integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity, feature exist
In: from top to bottom successively by substrate layer (1), transparent conductive anode layer (2), hole injection layer (3), exciton barrier-layer (4), donor
Layer (5), receptive layers (6), electron transfer layer (7) and electrode cathode layer (8) combine composition, and the donor layer (5) uses narrowband system
Any one material or any different materials having in the organic solar battery material absorbed by force are made, the receptive layers (6)
Using in fullerene or fullerene derivate material any one material or any different materials be made, the exciton barrier-layer
(4) with a thickness of 5-20nm, the material of the exciton barrier-layer (4) is the tool UV absorption of broad-band gap and hardly picks up visible
The hole mobile material of light, and the level-density parameter of the energy level of exciton barrier-layer (4) and the donor layer (5), above-mentioned each functional layer
It is prepared by the combination of any one technique or any mechanism technique for being all made of in rotary coating, printing, spraying and vapor deposition mode；
Exciton barrier-layer (4) material uses blue fluorescent material, green fluorescent material, blue phosphor materials and green phosphorescent
Any one material or any different materials in material, the blue fluorescent material use dark blue dyestuff 5- (4- (4,6-
diphenyl-1,3,5-triazin-2-yl)phenyl)-10,10-diphenyl-5,10-dihydrodibenzo[b,e]
[1,4]azasilin e(DTPDDA)、4,4’-Bis(2,2-diphenylvinyl)-1,1’-biphenyl(DPVBi)、
diphenyl-(4-{2-[4-(2-pyridin-4-yl-vinyl)-phenyl]-vinyl}-phenyl)-amine(DPVPA)、
2,7-bis[2-(4-tert-butylphenyl)pyrimidine-5-yl]-9,9’-spirobifluorene(TBPSF)、N,
- 1,1 '-biphenyl-4,4 '-diamine (<-NPD) of N '-diphenyl-N, N '-bis (1-naphthyl phenyl), 4,
4’-bis-9-carbozyl biphenyl(CBP)、4,4’-bis[(N-carbazole)styryl]biphenyl(BSB-
Cz)、2,4-bis{3-(9H-carbazol-9-yl)-9H-carbazol-9-yl}-6-phen yl-1,3,5-triazine
(CC2TA) any one material or any different materials in, the green fluorescent material using rhodamine 6G (R6G),
2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)
quinolizino-[9,9a,1gh]coumarin(C545T)、(4s,6s)-2,4,5,6-tetra(9H-carbazol-9-y
L) any one material or any different materials in isophthalonitrile (4CzIPN), the blue phosphor materials are adopted
With iridium bis (4,6-difloroPhenyl-pyridinato-N, C ') picolinate (Firpic), iridium
(Ⅲ)bis(4,6-difluorophenylpyridinato)tetrakis(1-pyraZolyl)borate(Fir6)、
Iridium(Ⅲ)bis(4,6-difluorophenyl-pyridinato)-5-(pyridine-2-yl)-1H-
Tetrazolate) any one material or any different materials in (FirN4)；The green phosphorescent material uses fac-
tris(2-phenylpyridine)iridium(Ir(ppy)3)、bis(2-phenyl pyridine)iridium(acet
yl-acetonate)((ppy)2Ir(acac))、tris[3,6-bis(phenyl)-pyridazinato-N1,C2’]iridium
(Ir(BPPya)3) in any one material or any different materials；
The material of the donor layer (5) is the boron subphthalocyanine chloride in narrowband system donor material
(SubPc)、copper phthalocyanine(CuPc)、chloroaluminium phthalocyanine(ClAlPc)、
zinc phthalocyanine(ZnPc)、rubrene、bis[2-(4-tertbutylphenyl)benzothiazolato-N,
C2’]iridium(acetylacetonate)(t-bt)2Ir(acac)4-(dicyano methylene)-2-t-butyl-6-
Any one material or any several in (1,1,7,7-tetramethyljulolidyl-9-enyl) -4H-pyran (DCJTB)
Kind material.
2. the organic solar of the integral type hole transmission layer according to claim 1 with exciton blocking and sunlight enhanced sensitivity
Battery, it is characterised in that: substrate composed by the transparent substrates (1) and transparent conductive anode (2) with a thickness of 100-
150nm, the hole injection layer (3) with a thickness of 5-10nm, the donor layer (5) with a thickness of 10-25nm, the receptive layers
(6) with a thickness of 30-50nm, the electron transfer layer (7) with a thickness of 5-10nm, the electrode cathode layer (8) with a thickness of
80-100nm。
3. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: the material of the substrate layer (1) is nonbreakable glass material, transparent polymer flexible material or life
Any one material or any several composite material in the flexible material of Biodegradable, wherein the transparent polymer is flexible
Material is polyethylene, polymethyl methacrylate, polycarbonate, polyurethanes, polyimides, polyamides resin and polypropylene
Any one material or any different materials in acid.
4. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: the material of the transparent conductive anode (2) is tin indium oxide (ITO), conducting polymer poly
(3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), graphene
(graphene), carbon nanotube (carbon nanotube), metal simple-substance, metal simple-substance nano wire, metal alloy nanowires,
Any one material or any different materials in metal hetero-junction nano wire.
5. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: the material of the hole injection layer (3) is MoO3、V2O5、NiO2、WO3In any one material
Or any different materials.
6. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: receptive layers (6) material is the C in fullerene or fullerene derivate material60、C70、[6,
6]-phenyl C71 butyric acid methyl ester(PC71BM)、[6,6]-phenyl C61butyric acid
methyl ester(PC61BM)、indene-C60 bisadduct(ICBA)、poly(9,9-dioctylfluorene-co-
Any one material or any different materials in benzothiadiazole (F8BT).
7. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: the material of the electron transfer layer (7) is graphene, carbon nanotube, ZnO, Cs2CO3、2,2',
2”-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole)(TPBi)、bathocuproine
(BCP), lithium Fluoride (LiF), tris- (8-hydroxyquinolinato) aluminum (Alq3), other evils
Diazoles compound, quinoxaline compound, the polymer of cyano-containing, other nitrogen-containing heterocycle compounds, organosilicon material, perfluor
Change material and any one material or any different materials in organic boron material.
8. the integral type hole transmission layer according to claim 1 or claim 2 with exciton blocking and sunlight enhanced sensitivity it is organic too
Positive energy battery, it is characterised in that: the electrode cathode layer (8) is any one material in Al, Ag, magnesium silver alloy and lithium-aluminium alloy
Material or any different materials.
9. a kind of organic solar of the integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity described in claim 1
The preparation method of battery, which comprises the following steps:
1) substrate composed by transparent substrates and transparent conductive anode is cleaned, is dried up after cleaning with drying nitrogen；
2) using rotary coating, printing, spraying or vapor deposition mode, and hole injection layer material is used, in the step 1)
Transparent conductive anode prepares hole injection layer on surface；
3) using rotary coating, printing, spraying or vapor deposition mode, and hole mobile material is used, the preparation in the step 2)
Hole injection layer surface on prepare exciton barrier-layer again；
4) using rotary coating, printing, spraying or vapor deposition mode, and organic electronic donor layer material is used, in the step 3)
Donor layer is prepared again in the exciton blocking layer surface of middle preparation；
5) using rotary coating, printing, spraying or vapor deposition mode, and electron acceptor layer material is used, the system in the step 4)
Receptive layers are prepared again in standby donor layer surface；
6) using rotary coating, printing, spraying or vapor deposition mode, and electron transport layer materials are used, the system in the step 5)
Electron transfer layer is prepared again in standby receptor layer surface；
7) it is masked plate replacement, evaporation cathode material, formation are electric again for the electron-transport layer surface prepared in the step 6)
Pole cathode layer, so that each functional layer of organic solar batteries be made.
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| CN106299133A (en) * | 2016-10-08 | 2017-01-04 | 吉林大学 | A kind of polymer solar battery based on metal oxide metal nanostructured hybrid electron transport layer and preparation method thereof |
| CN108695435B (en) * | 2018-05-21 | 2020-07-28 | 电子科技大学 | Organic solar cell based on ultrasonic annealing process and preparation method thereof |
| CN110534650B (en) * | 2019-05-28 | 2021-08-10 | 华南理工大学 | Self-filtering narrow-spectral-response organic photodetector |
| CN111180111A (en) * | 2020-01-14 | 2020-05-19 | 重庆烯宇新材料科技有限公司 | Silver nanowire transparent conductive film and flexible OLED |
| CN112885967B (en) * | 2021-01-28 | 2022-12-02 | 电子科技大学 | Double-layer organic solar cell based on delayed fluorescent material and preparation method |
| CN113838983B (en) * | 2021-08-26 | 2024-03-26 | 电子科技大学 | NPB/V-based 2 O 5 Organic photoelectric sensor of buffer layer and preparation method thereof |
| CN114695678B (en) * | 2022-02-28 | 2023-04-25 | 电子科技大学 | Method for effectively inhibiting dark current in organic photoelectric detector with inverted structure |
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