CN105655491A - Organic solar cell with exciton blocking and sunlight sensitivity enhancing integrated type hole transport layer and preparation method of organic solar cell - Google Patents
Organic solar cell with exciton blocking and sunlight sensitivity enhancing integrated type hole transport layer and preparation method of organic solar cell Download PDFInfo
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Abstract
The invention discloses an organic solar cell with an exciton blocking and sunlight sensitivity enhancing integrated type hole transport layer and a preparation method of the organic solar cell. The organic solar cell comprises a substrate, a transparent electrode, a hole injection layer, an exciton blocking layer, a donor layer, a receptor layer, an electronic transmitting layer and a negative electrode. The organic solar cell is characterized in that the exciton blocking layer can effectively block electrons at a positive electrode end through material matching, and dark current components and electron leakage currents of a photovoltaic cell are reduced; ultraviolet light in sunlight can be absorbed for emitting pure blue light or sky blue light, and the number of incidence photons of an active layer of the subsequent organic solar cell is increased. Photo-generated currents are increased for improving the power conversion efficiency of a photovoltaic cell. The organic solar cell achieves dual functions of exciton blocking and sunlight enhancing at the same time through a simple method without other additional optical design or complex processes. The organic solar cell is simple in preparation process, low in device requirement and suitable for mass production.
Description
Technical field
The present invention relates to a kind of organic optoelectronic device and preparation method thereof, particularly relate to a kind of organic solar batteries (OPV) and preparation method thereof, be applied to green solar source technology field.
Background technology
Organic optoelectronic technology is that Jin10Nian Lai world academia develops one of swift and violent high-tech. Multiformity along with the fast development of film technique and organic material or organic/inorganic hybridization material design, organic electroluminescence device, organic solar batteries (organicphotovoltaiccell, OPV), the organic optoelectronic product such as organic field effect tube be developing progressively ripe, and have be prone to large area prepare, the advantage such as flexibility, shock pressure. Wherein, utilize the organic solar batteries of clean energy resource by its advantage such as environmental protection, low cost, attract tremendous attention at energy technology field; Organic molecule/polymeric material and easy film-forming process is adopted to have been achieved for the photoelectric transformation efficiency breakthrough more than 12%, for alleviating the exhaustion of fossil energy and ensureing that the sustainable development of human society provides good solution. Especially the planar heterojunction in OPV is due to its simple in construction, and material purity is less demanding, is therefore the first-selection of researcher desk study material behavior and device architecture performance.
But, traditional OPV device suffer drawbacks that:
1. solar spectrum medium ultraviolet light, visible ray, infrared light ratio fix, as the light intensity of certain part need to be strengthened, need to be designed or prepare the micro-nano structure of Special complex by physical optics to reach optically focused or strengthen the purpose of reflection and refraction or widen the absorption to sunlight by the tandem type OPV (cascadeOPV) of design complex configurations;
2. giving in the traditional planar heterojunction battery/exciton dissociation of receptor is abundant not, causes that short circuit current is on the low side;
3. in bulk heterojunction, appearance structure is complicated, it is more difficult to accurately control, and the not clear part of mechanism is more;
4. the injection of hole and electronics and transfer rate are not mated and are caused that the photogenerated current of final generation is limited.
Hole traditional in OPV is injected or transmission material is poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), there is excellent smooth electrically-conductive backing plate, leakage current is suppressed to obtain the effect of relatively high open circuit voltage, but be also strong Exciton quenching agent, this have impact on the OPV popularization in real world applications field. simultaneously
Summary of the invention
In order to solve prior art problem, it is an object of the invention to the deficiency overcoming prior art to exist, a kind of organic solar batteries of integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity and preparation method thereof is provided, adopt and increase anode tap exciton barrier-layer, the NEW TYPE OF COMPOSITE functional layer structure of transparent anode-hole injection layer-exciton barrier-layer-donor layer is formed in OPV, enable integral type hole transmission layer to realize exciton simultaneously and stop the effect with sunlight enhanced sensitivity, present invention process is simple, save material simultaneously, reduce cost, there is great industrial value.
Create purpose for reaching foregoing invention, insight of the invention is that
Create the organic solar batteries device based on the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, device is mainly characterized by the optical design of complexity that need not be extra or prepares micro-nano structure to strengthen sunlight intensity or to provide favourable reflection and refraction, this hole transmission layer can absorb ultraviolet light emission blue light or green glow thus additionally increasing incident illumination photon numbers, and have 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 mates with donor layer device open-circuit voltage is had no adverse effects, and higher hole mobility will not constraint device fill factor, curve factor. By reasonably selecting material, realize exciton dexterously simultaneously and stop and sunlight sensitization.
Conceive according to foregoing invention, adopt following technical proposals:
A kind of organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, from top to bottom successively by substrate layer, transparent conductive anode layer, hole injection layer, exciton barrier-layer, donor layer, receptive layers, electron transfer layer and electrode cathode layer combine composition, donor layer adopts any one material in the organic solar battery material that arrowband cording absorbs by force or any different materials to make, receptive layers adopts any one material in fullerene or fullerene derivate material or any different materials to make, the thickness of exciton barrier-layer is 5-20nm, the material of exciton barrier-layer is the tool uv absorption of broad-band gap and hardly picks up the hole mobile material of visible ray, and the level-density parameter of the energy level of exciton barrier-layer and donor layer.
The thickness of the substrate that above-mentioned transparent substrates and transparent conductive anode form is 100-150nm, the thickness of above-mentioned hole injection layer is preferably 5-10nm, the thickness of above-mentioned donor layer is preferably 10-25nm, the thickness of above-mentioned receptive layers is preferably 30-50nm, the thickness of above-mentioned electron transfer layer is preferably 5-10nm, and the thickness of above-mentioned electrode cathode layer is preferably 80-100nm.
Above-mentioned exciton barrier-layer material preferably employs any one material in blue fluorescent material, green fluorescent material, blue phosphor materials and green phosphorescent material or any different materials, blue fluorescent material adopts 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-naphthylphenyl)-1, 1 '-biphenyl-4, 4 '-diamine (��-NPD), N, N '-diphenyl-N, N '-bis (1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamine (NPB), 4, 4 '-bis-9-carbozylbiphenyl (CBP), 4, 4 '-bis [(N-carbazole) styryl] biphenyl (BSB-Cz), 2, 4-bis{3-(9H-carbazol-9-yl)-9H-carbazol-9-yl}-6-phenyl-1, 3, any one material in 5-triazine (CC2TA) or arbitrarily different materials,Green fluorescent material adopt rhodamine6G (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-yl) any one material in isophthalonitrile (4CzIPN) or any different materials; Blue phosphor materials adopts iridiumbis (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 in (FirN4) or any different materials; Green phosphorescent material adopts fac-tris (2-phenylpyridine) iridium (Ir (ppy)3)��bis(2-phenylpyridine)iridium(acetyl-acetonate)((ppy)2Ir (acac)) and tris [3,6-bis (phenyl)-pyridazinato-N1,C2��]iridium(Ir(BPPya)3) in any one material or any different materials.
The material of above-mentioned substrate layer is preferably any one material in nonbreakable glass material, transparent polymer flexible material or biodegradable flexible material or arbitrarily several composites, and wherein transparent polymer flexible material is any one material in polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, polyamides resin and polyacrylic acid or any different materials.
The material of above-mentioned transparent conductive anode is preferably any one material in tin indium oxide (ITO), conducting polymer poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), Graphene (graphene), CNT (carbonnanotube), metal simple-substance, metal simple-substance nano wire, metal alloy nanowires, metal hetero-junction nano wire or any different materials.
The material of above-mentioned hole injection layer is preferably MoO3��V2O5��NiO2��WO3In any one material or any different materials.
The material of above-mentioned donor layer is preferably the boronsubphthalocyaninechloride (SubPc) in arrowband system donor material, copperphthalocyanine (CuPc), chloroaluminiumphthalocyanine (ClAlPc), zincphthalocyanine (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 in-4H-pyran (DCJTB) or arbitrarily different materials.
Above-mentioned receptive layers material is preferably the C in fullerene or fullerene derivate material60��C70, [6,6]-phenylC71butyricacidmethylester (PC71BM), [6,6]-phenylC61butyricacidmethylester (PC61BM), indene-C60bisadduct (ICBA), poly (any one material in 9,9-dioctylfluorene-co-benzothiadiazole (F8BT) or arbitrarily different materials.
The material of above-mentioned electron transfer layer is preferably Graphene, CNT, ZnO, Cs2CO3, 2,2'; 2 "-(1,3,5-benzinetriyl) any one material in-tris (1-phenyl-1-H-benzimidazole) (TPBi), bathocuproine (BCP), lithiumFluoride (LiF), tris-(8-hydroxyquinolinato) aluminum (Alq3), other diazoles compounds, quinoxaline compound, the polymer of cyano-containing, other nitrogen-containing heterocycle compounds, organosilicon material, perfluorinated material and organic boron material or arbitrarily different materials.
Above-mentioned electrode cathode layer is preferably any one material in Al, Ag, magnesium silver alloy and lithium-aluminium alloy or any different materials.
The preparation method that a kind of present invention has the organic solar batteries of the integral type hole transmission layer of exciton stop and sunlight enhanced sensitivity, it is characterised in that comprise the following steps:
1) substrate that transparent substrates and transparent conductive anode are formed is carried out, and dries up with drying nitrogen after cleaning;
2) adopt rotary coating, printing, spraying or evaporation mode, and adopt hole injection layer material, in step 1) in transparent conductive anode surface on prepare hole injection layer;
3) adopt rotary coating, printing, spraying or evaporation mode, and adopt hole mobile material, in step 2) in preparation hole injection layer surface on prepare exciton barrier-layer again;
4) adopt rotary coating, printing, spraying or evaporation mode, and adopt organic electronic donor layer material, in step 3) in preparation exciton barrier-layer surface on prepare donor layer again;
5) adopt rotary coating, printing, spraying or evaporation mode, and adopt electron acceptor layer material, in step 4) in preparation donor layer surface on prepare receptive layers again;
6) adopt rotary coating, printing, spraying or evaporation mode, and adopt electron transport layer materials, in step 5) in preparation receptive layers surface on prepare electron transfer layer again;
7) it is masked plate to change, in step 6) the middle electron transfer layer surface evaporation cathode material again prepared, form electrode cathode layer, thus making each functional layer of organic solar batteries.
The present invention is in the transparency electrode of device based on the preparation method of the organic solar batteries device of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, by being sequentially depositing hole injection layer, hole transmission layer and exciton barrier-layer, then on exciton barrier-layer, it is sequentially depositing donor layer, receptive layers and electron transfer layer, finally on the electron transport layer by vacuum vapour deposition depositing electrode negative electrode by vacuum evaporation, spin coating or print process. The present invention inserts the exciton barrier-layer of a broad-band gap between hole injection layer and donor material can effectively prevent Exciton quenching, reduces dark current component and the electron leakage current of photovoltaic cell. Additionally being added with of exciton barrier-layer is beneficial to the transmission performance balancing hole and electronics, makes the more active layer that is limited in electron hole be separated, thus strengthening photoelectric current. Additionally by reasonably select material, be deposited on the exciton barrier-layer of sunlight incidence end can absorb ultraviolet light produce can by the visible ray of/acceptor material absorption thus increasing the incident photon quantity of consequent activities layer, this is a kind of simple and effective enhanced sensitivity sunlight thus the method that improves photogenerated current.
The present invention compared with prior art, has following apparent prominent substantive distinguishing features and remarkable advantage:
1., relative to traditional OPV structure with single hole injection layer, the exciton barrier-layer in device of the present invention is provided simultaneously with stopping electronics, prevents Exciton quenching, reduces dark current component and electron leakage current and transmitting blue light or green glow to strengthen the effect of incident sunlight photon numbers;
2. the present invention is by rationally selecting exciton barrier-layer material, so as to energy level mate with donor layer, emission spectrum mates with to the absorption spectrum of/receptive layers, and the light of itself absorption does not affect the absorption of active layer;
3. the performance of whole device is played an important role by the exciton barrier-layer THICKNESS CONTROL that prepared by the present invention, and the thickness optimum control of exciton barrier-layer, at 5-20nm, too thin too thick all can reduce shorted devices electric current and fill factor, curve factor;
4. device architecture of the present invention is simple, and exciton barrier-layer thickness and composition can accurately control, it is possible to obtain stable performance, is thus advantageous to preparation cascade OPV device or volume production.
Accompanying drawing explanation
Fig. 1 is the structural representation of various embodiments of the present invention organic solar batteries.
Fig. 2 is the absorptance characteristic curve of the different exciton barrier-layer NPB of various embodiments of the present invention and BSB-Cz monofilm.
Fig. 3 is the fluorescence spectrum normalization characteristic curve of the different exciton barrier-layer NPB of various embodiments of the present invention and BSB-Cz monofilm.
Fig. 4 is donor DBP, SubPc and the receptor C of various embodiments of the present invention60The absorptance characteristic curve of monofilm.
Detailed description of the invention
Details are as follows for the preferred embodiments of the present invention:
Embodiment one:
In the present embodiment, referring to Fig. 1, a kind of organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, 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 88 one functional layer altogether combine composition, donor layer 5 adopts the organic solar battery material that arrowband cording absorbs by force to make, receptive layers 6 adopts fullerene to make, the material of exciton barrier-layer 4 is the tool uv absorption of broad-band gap and hardly picks up the hole mobile material of visible ray, and the level-density parameter of the energy level of exciton barrier-layer 4 and donor layer 5.
In the present embodiment, adopt the ito substrate that substrate layer 1 and transparent conductive anode layer 2 form, ito substrate thickness is 150nm, namely select the transparent IT0 glass substrate being etched into a solid plate as anode, successively with lotion, acetone, deionized water, isopropanol ultrasonic cleaning 20 minutes, nitrogen dries up, UV/O3Process 15 minutes standby. By the method for vacuum evaporation, IT0 glass substrate deposits MoO3Prepare the hole injection layer 3 that thickness is 5nm, then deposition NPB prepare the exciton barrier-layer 4 that thickness is 5-10nm, following deposit thickness be the donor red dye DBP of 10-20nm to prepare donor layer 5, then deposit thickness is the C of 30-50nm60Prepare receptive layers 6, then the electron transport layer materials Bphen that deposit thickness is 5-10nm prepares electron transfer layer 7, finally change mask plate with evaporation cathode metal Al, prepare the electrode cathode layer 8 that thickness is 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 absworption peak of NPB is 348nm, and emission peak is 438nm. Donor layer DBP and receptive layers C60Absorption spectrum see Fig. 4. The blue light that NPB launches is just at C60With the absorption region of DBP, additionally enhance sunlight intensity, and do not affect to/the receptor absorption to visible ray itself.
The present embodiment is prepared for the organic solar batteries of a kind of integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, the feature part of this device is in that exciton barrier-layer, pass through match materials, this exciton barrier-layer can realize the electronics effective stop at anode tap, reduces dark current component and the electron leakage current of photovoltaic cell; Sunlight middle-ultraviolet lamp can be absorbed again and launch ethereal blue or sky blue light, enhance follow-up organic solar batteries active layer namely to the incident photon quantity of/receptive layers. Two aspects all can improve photogenerated current to improve the power conversion efficiency of photovoltaic cell. The present embodiment OPV device, when without the design of other extra optical and complicated technology, is simultaneously achieved, by a kind of simple method, the double effects that exciton stops and sunlight strengthens. The present embodiment preparation technology is simple, equipment requirements is low, be suitable for volume production.
Embodiment two:
The present embodiment is essentially identical with embodiment one, is particular in that:
In the present embodiment, referring to Fig. 1, selecting the transparent IT0 glass substrate being etched into a solid plate as anode, IT0 thickness of glass substrate is 150nm.Successively with lotion, acetone, deionized water, isopropanol ultrasonic cleaning 20 minutes, nitrogen dries up, UV/O3Process 15 minutes standby. By the method for vacuum evaporation, deposition of hole implanted layer MoO on IT0 glass substrate3, thickness is 10nm, then deposition exciton barrier-layer BSB-Cz, and THICKNESS CONTROL is at 8-20nm, and next deposition donor SubPc, thickness is 7-20nm and receptive layers C60, thickness is 30-50nm, then deposits electron transport layer materials Bphen, and thickness is 5-10nm, then changes mask plate with evaporation cathode metal, and evaporation metal Al is negative electrode, and thickness is 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 absworption peak of BSB-Cz is 370nm, and emission peak is 478nm. Donor layer SubPc and receptive layers C60Absorption spectrum see Fig. 4. The blue green light that BSB-Cz launches is just at SubPc and C60Absorption region, additionally enhance sunlight intensity, simultaneously work as electronic blocking effect.
The present embodiment is also by match materials, and same hole transmission layer can realize exciton simultaneously to be stopped and strengthens follow-up to effect of/incident intensity of receptive layers. Having low cost, structural manufacturing process is simple, and the feature such as can prepare on flexible substrates. Can obtain in solar electrical energy generation and be widely applied.
Above in conjunction with accompanying drawing, the embodiment of the present invention is illustrated, but the invention is not restricted to above-described embodiment, multiple change can also be made according to the purpose of the innovation and creation of the present invention, the change made under all spirit according to technical solution of the present invention and principle, modify, substitute, combination or simplification, all should be the substitute mode of equivalence, as long as meeting the goal of the invention of the present invention, the know-why of the organic solar batteries of integral type hole transmission layer without departing from the present invention with exciton stop and sunlight enhanced sensitivity and preparation method thereof and inventive concept, broadly fall into protection scope of the present invention.
Claims (11)
1. the organic solar batteries of an integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity, it is characterized in that: 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, described donor layer (5) adopts any one material in the organic solar battery material that arrowband cording absorbs by force or any different materials to make, described receptive layers (6) adopts any one material in fullerene or fullerene derivate material or any different materials to make, the thickness of described exciton barrier-layer (4) is 5-20nm, the material of described exciton barrier-layer (4) is the tool uv absorption of broad-band gap and hardly picks up the hole mobile material of visible ray, and the level-density parameter of the energy level of exciton barrier-layer (4) and described donor layer (5).
2. there is the organic solar batteries of the integral type hole transmission layer of exciton stop and sunlight enhanced sensitivity according to claim 1, it is characterized in that: the thickness of the substrate that described transparent substrates (1) and transparent conductive anode (2) form is 100-150nm, the thickness of described hole injection layer (3) is 5-10nm, the thickness of described donor layer (5) is 10-25nm, the thickness of described receptive layers (6) is 30-50nm, the thickness of described electron transfer layer (7) is 5-10nm, and the thickness of described electrode cathode layer (8) is 80-100nm.
3. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterized in that: described exciton barrier-layer (4) material adopts any one material in blue fluorescent material, green fluorescent material, blue phosphor materials and green phosphorescent material or any different materials, described blue fluorescent material adopts 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-naphthylphenyl)-1, 1 '-biphenyl-4, 4 '-diamine (<-NPD), N, N '-diphenyl-N, N '-bis (1-naphthyl)-1, 1 '-biphenyl-4, 4 '-diamine (NPB), 4, 4 '-bis-9-carbozylbiphenyl (CBP), 4, 4 '-bis [(N-carbazole) styryl] biphenyl (BSB-Cz), 2, 4-bis{3-(9H-carbazol-9-yl)-9H-carbazol-9-yl}-6-phenyl-1, 3, any one material in 5-triazine (CC2TA) or arbitrarily different materials, described green fluorescent material adopts rhodamine6G (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-yl) any one material in isophthalonitrile (4CzIPN) or any different materials, described blue phosphor materials adopts iridiumbis (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 in (FirN4) or any different materials, described green phosphorescent material adopts fac-tris (2-phenylpyridine) iridium (Ir (ppy)3)��bis(2-phenylpyridine)iridium(acetyl-acetonate)((ppy)2Ir(acac))��tris[3,6-bis(phenyl)-pyridazinato-N1,C2��]iridium(Ir(BPPya)3) in any one material or any different materials.
4. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterized in that: the material of described substrate layer (1) is any one material in nonbreakable glass material, transparent polymer flexible material or biodegradable flexible material or arbitrarily several composites, wherein said transparent polymer flexible material is any one material in polyethylene, polymethyl methacrylate, Merlon, polyurethanes, polyimides, polyamides resin and polyacrylic acid or any different materials.
5. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterized in that: the material of described transparent conductive anode (2) is tin indium oxide (ITO), conducting polymer poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), Graphene (graphene), CNT (carbonnanotube), metal simple-substance, metal simple-substance nano wire, metal alloy nanowires, any one material in metal hetero-junction nano wire or arbitrarily different materials.
6. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterised in that: the material of described hole injection layer (3) is MoO3��V2O5��NiO2��WO3In any one material or any different materials.
7. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterized in that: the material of described donor layer (5) is the boronsubphthalocyaninechloride (SubPc) in arrowband system donor material, copperphthalocyanine (CuPc), chloroaluminiumphthalocyanine (ClAlPc), zincphthalocyanine (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 in-4H-pyran (DCJTB) or arbitrarily different materials.
8. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterised in that: described receptive layers (6) material is the C in fullerene or fullerene derivate material60��C70, [6,6]-phenylC71butyricacidmethylester (PC71BM), [6,6]-phenylC61butyricacidmethylester (PC61BM), indene-C60bisadduct (ICBA), poly (any one material in 9,9-dioctylfluorene-co-benzothiadiazole (F8BT) or arbitrarily different materials.
9. the organic solar batteries of the integral type hole transmission layer with exciton stop and sunlight enhanced sensitivity according to claim 1 or claim 2, it is characterised in that: the material of described electron transfer layer (7) is Graphene, CNT, ZnO, Cs2CO3, 2,2'; 2 "-(1,3,5-benzinetriyl) any one material in-tris (1-phenyl-1-H-benzimidazole) (TPBi), bathocuproine (BCP), lithiumFluoride (LiF), tris-(8-hydroxyquinolinato) aluminum (Alq3), other diazoles compounds, quinoxaline compound, the polymer of cyano-containing, other nitrogen-containing heterocycle compounds, organosilicon material, perfluorinated material and organic boron material or arbitrarily different materials.
10. according to claim 1 or claim 2 have exciton and stop and the organic solar batteries of integral type hole transmission layer of sunlight enhanced sensitivity, it is characterised in that: described electrode cathode layer (8) is Al, any one material in Ag, magnesium silver alloy and lithium-aluminium alloy or any different materials.
11. the preparation method described in a claim 1 with the organic solar batteries of the integral type hole transmission layer of exciton stop and sunlight enhanced sensitivity, it is characterised in that comprise the following steps:
1) substrate that transparent substrates and transparent conductive anode are formed is carried out, and dries up with drying nitrogen after cleaning;
2) adopt rotary coating, printing, spraying or evaporation mode, and adopt hole injection layer material, in described step 1) in transparent conductive anode surface on prepare hole injection layer;
3) adopt rotary coating, printing, spraying or evaporation mode, and adopt hole mobile material, in described step 2) in preparation hole injection layer surface on prepare exciton barrier-layer again;
4) adopt rotary coating, printing, spraying or evaporation mode, and adopt organic electronic donor layer material, in described step 3) in preparation exciton barrier-layer surface on prepare donor layer again;
5) adopt rotary coating, printing, spraying or evaporation mode, and adopt electron acceptor layer material, in described step 4) in preparation donor layer surface on prepare receptive layers again;
6) adopt rotary coating, printing, spraying or evaporation mode, and adopt electron transport layer materials, in described step 5) in preparation receptive layers surface on prepare electron transfer layer again;
7) it is masked plate to change, in described step 6) the middle electron transfer layer surface evaporation cathode material again prepared, form electrode cathode layer, thus making each functional layer of organic solar batteries.
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