CN105655491B - The organic solar batteries and preparation method thereof of integral type hole transmission layer with exciton blocking and sunlight enhanced sensitivity - Google Patents

Abstract

The invention discloses an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization and a preparation method thereof. The device includes a substrate, a transparent electrode, a hole injection layer, an exciton blocking layer, Donor layer, acceptor layer, electron transport layer and electrode cathode. The device is characterized by an exciton blocking layer. Through material matching, this exciton blocking layer can not only effectively block electrons at the anode end, reduce the dark current component and electron leakage current of photovoltaic cells; The ultraviolet light emits pure blue or sky blue light, enhancing the number of incident photons to the active layer of the subsequent organic solar cell. The photogenerated current is increased to improve the power conversion efficiency of photovoltaic cells. The device disclosed by the invention simultaneously realizes the dual effects of exciton blocking and solar light enhancement in a simple method without additional optical design and complicated process. The preparation process is simple, the equipment requirement is low, and it is suitable for mass production.

Description

Organic solar cells with an integrated hole-transporting layer for exciton blocking and solar light sensitization Energy battery and preparation method thereof

technical field

The invention relates to an organic optoelectronic device and a preparation method thereof, in particular to an organic solar cell (OPV) and a preparation method thereof, which are applied in the technical field of green solar energy.

Background technique

Organic optoelectronic technology is one of the high-tech technologies that have developed rapidly in the world's academic circles in the past 10 years. With the rapid development of film-forming technology and the diversity of design of organic materials or organic/inorganic hybrid materials, organic optoelectronic products such as organic electroluminescence devices, organic solar cells (organic photovoltaic cells, OPV), organic field effect transistors, etc. are gradually developing. Mature, and has the advantages of easy large-area preparation, flexibility, and shock resistance. Among them, organic solar cells using clean energy have attracted much attention in the field of energy technology due to their advantages of environmental protection and low cost; the use of small organic molecules/polymer materials and simple film formation processes have achieved photoelectric conversion efficiency exceeding 12%. The breakthrough progress of this technology provides a good solution for alleviating the depletion of fossil energy and ensuring the sustainable development of human society. In particular, the planar heterojunction in OPV has a simple structure and does not require high material purity, so it is the first choice for researchers to initially explore material properties and device structural performance.

However, traditional OPV devices have some disadvantages:

1. The ratio of ultraviolet light, visible light, and infrared light in the solar spectrum is fixed. If it is necessary to enhance the light intensity of a certain part, it is necessary to design or prepare special and complex micro-nano structures through physical optics to achieve the purpose of concentrating light or enhancing reflection and refraction. Or broaden the absorption of sunlight by designing a cascade OPV (cascade OPV) with a complex structure;

2. The donor/acceptor exciton separation in traditional planar heterojunction cells is not sufficient, resulting in low short-circuit current;

3. The morphology and structure of the bulk heterojunction are complex, it is difficult to control accurately, and there are many unknown mechanisms;

4. The mismatch between the injection and transport rates of holes and electrons leads to the limitation of the final photogenerated current.

The traditional hole injection or transport material in OPV is poly(3,4-ethylenedioxythiophene):poly(tyrenesulfonate) (PEDOT:PSS), which has an excellent smooth conductive substrate, suppresses leakage current and obtains a higher open circuit voltage, but at the same time It is also a strong exciton quencher, which affects the promotion of OPV in practical applications.

Contents of the invention

In order to solve the problems of the prior art, the object of the present invention is to overcome the deficiencies of the prior art, and provide an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization and a preparation method thereof. Exciton blocking layer at the anode end, forming a new composite functional layer structure of transparent anode-hole injection layer-exciton blocking layer-donor layer in OPV, so that the integrated hole transport layer can simultaneously realize exciton blocking and sunlight Sensitization effect, the invention has a simple process, saves materials and reduces costs at the same time, and has great industrial value.

In order to achieve the above-mentioned invention creation purpose, design of the present invention is:

Create an organic solar cell device based on an integrated hole transport layer with exciton blocking and solar light sensitization. The main feature of the device is that it does not require additional complex optical design or preparation of micro-nano structures to enhance the intensity of sunlight or provide favorable Reflection and refraction, this hole transport layer can absorb ultraviolet light and emit blue or green light to additionally increase the number of incident light photons, and at the same time have an electron blocking effect. The structure of the device is simple, the single hole transport layer has two functions at the same time, and the matching of its energy level and the donor layer has no adverse effect on the open circuit voltage of the device, and the higher hole mobility will not restrict the device fill factor. Through reasonable selection of materials, exciton blocking and solar light sensitization can be cleverly realized at the same time.

According to above-mentioned inventive concept, adopt following technical scheme:

An organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization, which consists of a substrate layer, a transparent conductive anode layer, a hole injection layer, an exciton blocking layer, and a donor layer from bottom to top , acceptor layer, electron transport layer and electrode cathode layer, the donor layer is made of any material or any several materials in organic solar cell materials with narrow band and strong absorption, and the acceptor layer is made of fullerene or any one of the fullerene derivative materials or any several materials, the thickness of the exciton blocking layer is 5-20nm, and the material of the exciton blocking layer is a wide band gap with ultraviolet absorption and almost no absorption of visible light The hole transport material, and the energy level of the exciton blocking layer matches the energy level of the donor layer.

The thickness of the substrate composed of the above-mentioned transparent substrate and transparent conductive anode is 100-150 nm, the thickness of the above-mentioned hole injection layer is preferably 5-10 nm, the thickness of the above-mentioned donor layer is preferably 10-25 nm, and the thickness of the above-mentioned acceptor layer It is preferably 30-50 nm, the thickness of the above-mentioned electron transport layer is preferably 5-10 nm, and the thickness of the above-mentioned electrode cathode layer is preferably 80-100 nm.

The above-mentioned exciton blocking layer material preferably adopts any one material or any several materials in blue fluorescent material, green fluorescent material, blue phosphorescent material and green phosphorescent material, and blue fluorescent material adopts dark blue dye 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 (α-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-1,3,5-triazine (CC2TA) any one material or any several materials; green fluorescent material adopts 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(4CzIPN) any one or several materials; blue phosphorescent material adopts With 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) (FirN4) any one material or any several materials; the green phosphorescent material adopts fac-tris(2 -phenylpyridine) iridium (Ir(ppy) ₃ ), bis(2-phenylpyridine) iridium(acetyl-acetonate) ((ppy) ₂ Ir(acac)) and tris[3,6-bis(phenyl)-pyridazinato-N ₁ , C ₂ ']iridium (Ir(BPP ya) ₃ ) any one material or any several materials.

The material of the above-mentioned substrate layer is preferably any one of rigid glass material, transparent polymer flexible material or biodegradable flexible material or any composite material, wherein the transparent polymer flexible material is polyethylene, polymethyl Any one material or any several materials among methyl acrylate, polycarbonate, polyurethane, polyimide, polyamide resin and polyacrylic acid.

The material of the above-mentioned transparent conductive anode is preferably indium tin oxide (ITO), conductive polymer poly(3,4-ethylenedioxy thiophene): poly(styrenesulfonate) (PEDOT:PSS), graphene (graphene), carbon nanotube (carbon nanotube) ), metal element, metal element nanowire, metal alloy nanowire, metal heterojunction nanowire any one material or any several materials.

The material of the above-mentioned hole injection layer is preferably any one material or any several materials among MoO ₃ , V ₂ O ₅ , NiO ₂ , WO ₃ .

The material of the above-mentioned donor layer is preferably boron subphthalocyanine 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) -4H-pyran (DCJTB) any one material or any several materials.

The above-mentioned acceptor layer material is preferably C ₆₀ , C ₇₀ , [6,6]-phenylC71 butyric acid methyl ester (PC71BM), [6,6]-phenyl C61 butyric acid in fullerene or fullerene derivative materials Any one or several of methylester (PC61BM), indene-C60 bisadduct (ICBA), poly(9,9-dioctylfluorene-co-benzothiadiazole (F8BT)

The material of the electron transport layer is preferably graphene, carbon nanotubes, ZnO, Cs ₂ CO ₃ , 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 oxadiazole compounds, quinoxaline compounds, cyano-containing polymers, others Any one or several of nitrogen-containing heterocyclic compounds, organic silicon materials, perfluorinated materials and organic boron materials.

The cathode layer of the above-mentioned electrode is preferably any one material or any several materials among Al, Ag, magnesium-silver alloy and lithium-aluminum alloy.

A method for preparing an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization of the present invention, is characterized in that it comprises the following steps:

1) Clean the substrate composed of the transparent substrate and the transparent conductive anode, and dry it with dry nitrogen after cleaning;

2) Prepare a hole injection layer on the surface of the transparent conductive anode in step 1) by using spin coating, printing, spray coating or evaporation, and using a hole injection layer material;

3) Using spin coating, printing, spraying or evaporation, and using a hole transport material, an exciton blocking layer is prepared on the surface of the hole injection layer prepared in step 2);

4) Using spin coating, printing, spraying or evaporation, and using an organic electron donor layer material, preparing a donor layer on the surface of the exciton blocking layer prepared in step 3);

5) Using spin coating, printing, spraying or evaporation, and using the electron acceptor layer material, preparing an acceptor layer on the surface of the donor layer prepared in step 4);

6) Using spin coating, printing, spraying or evaporation, and using electron transport layer materials, an electron transport layer is prepared on the surface of the acceptor layer prepared in step 5);

7) The mask plate is replaced, and the cathode material is evaporated on the surface of the electron transport layer prepared in step 6) to form an electrode cathode layer, thereby making each functional layer of the organic solar cell.

The preparation method of the organic solar cell device based on the integrated hole transport layer with exciton blocking and solar light sensitization is to deposit the hole injection layer and the hole transport layer in sequence on the transparent electrode of the device. The barrier layer, and then on the exciton blocking layer, the donor layer, the acceptor layer and the electron transport layer are sequentially deposited by vacuum evaporation, spin coating, or printing, and finally the electrode cathode is deposited on the electron transport layer by vacuum evaporation. . The present invention inserts a wide bandgap exciton blocking layer between the hole injection layer and the donor material, which can effectively prevent excitons from quenching and reduce the dark current component and electron leakage current of the photovoltaic cell. In addition, the addition of the exciton blocking layer is beneficial to balance the transport properties of holes and electrons, so that the electron holes are more confined in the active layer and separated, thereby enhancing the photocurrent. In addition, through reasonable selection of materials, the exciton blocking layer deposited on the incident side of sunlight can absorb ultraviolet light to generate visible light that can be absorbed by the donor/acceptor material, thereby increasing the number of incident photons in the subsequent active layer, which is a simple and effective sensitization method. Sunlight thereby increasing the photogenerated current method.

Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:

1. Compared with the traditional OPV structure with a single hole injection layer, the exciton blocking layer in the device of the present invention has the functions of blocking electrons, preventing exciton quenching, reducing dark current components and electron leakage current, and emitting blue or green light To enhance the effect of the number of photons of incident sunlight;

2. The present invention matches the energy level of the donor layer and the emission spectrum with the absorption spectrum of the donor/acceptor layer by rationally selecting the material of the exciton blocking layer, and its own light absorption does not affect the absorption of the active layer;

3. The thickness control of the exciton blocking layer prepared by the present invention plays an important role in the performance of the entire device, and the thickness of the exciton blocking layer is optimally controlled at 5-20nm, too thin or too thick will reduce the short circuit current and fill factor of the device;

4. The structure of the device of the present invention is simple, the thickness and composition of the exciton blocking layer can be precisely controlled, and stable performance can be obtained, so it is beneficial to the preparation of cascaded OPV devices or mass production.

Description of drawings

FIG. 1 is a schematic structural view of an organic solar cell according to various embodiments of the present invention.

Fig. 2 is the characteristic curves of absorption coefficients of different exciton blocking layers NPB and BSB-Cz single films in various embodiments of the present invention.

Fig. 3 is the normalized characteristic curves of fluorescence spectra of different exciton blocking layers NPB and BSB-Cz single films of various embodiments of the present invention.

Fig. 4 is the characteristic curves of absorption coefficients of donor DBP, SubPc and acceptor C ₆₀ single membranes in various embodiments of the present invention.

Detailed ways

Preferred embodiments of the present invention are described in detail as follows:

Embodiment one:

In this embodiment, referring to FIG. 1 , an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization consists of a substrate layer 1 , a transparent conductive anode layer 2 , and a hole layer from bottom to top. The hole injection layer 3, the exciton blocking layer 4, the donor layer 5, the acceptor layer 6, the electron transport layer 7 and the electrode cathode layer 8 are composed of a total of 8 functional layers. made of solar cell materials, the acceptor layer 6 is made of fullerene, the material of the exciton blocking layer 4 is a wide bandgap hole transport material with ultraviolet absorption and almost no absorption of visible light, and the energy of the exciton blocking layer 4 The level matches the energy level of the donor layer 5.

In this embodiment, the ITO substrate composed of the substrate layer 1 and the transparent conductive anode layer 2 is used, and the thickness of the ITO substrate is 150nm, that is, a transparent ITO glass substrate etched into a certain template is selected as the anode, and the anode is sequentially washed with lotion, acetone , deionized water, and isopropanol ultrasonic cleaning for 20 minutes, blown dry with nitrogen, and treated with UV/O ₃ for 15 minutes for later use. By vacuum evaporation, deposit MoO ₃ on the ITO glass substrate to prepare a hole injection layer 3 with a thickness of 5nm, then deposit NPB to prepare an exciton blocking layer 4 with a thickness of 5-10nm, and then deposit a thickness of 10-20nm The donor red light dye DBP is used to prepare the donor layer 5, and then the C ₆₀ with a thickness of 30-50nm is deposited to prepare the acceptor layer 6, and the electron transport layer material Bphen with a thickness of 5-10nm is deposited to prepare the electron transport layer 7, Finally, the mask plate is replaced to vapor-deposit cathode metal Al to prepare electrode cathode layer 8 with a thickness of 80-100 nm.

The absorption and emission spectra of the exciton blocking layer NPB of this embodiment are shown in Fig. 2 and Fig. 3 respectively. The absorption peak of NPB is 348nm and the emission peak is 438nm. The absorption spectra of the donor layer DBP and the acceptor layer C ₆₀ are shown in FIG. 4 . The blue light emitted by NPB is just in the absorption range of C ₆₀ and DBP, which additionally enhances the intensity of sunlight without affecting the absorption of visible light by the donor/acceptor itself.

In this example, an organic solar cell with an integrated hole-transporting layer for exciton blocking and sunlight sensitization is prepared. The device is characterized by an exciton blocking layer. It can realize the effective blocking of electrons at the anode end, reduce the dark current component and electron leakage current of photovoltaic cells; it can also absorb ultraviolet rays in sunlight and emit pure blue or sky blue light, which enhances the active layer of subsequent organic solar cells, that is, the donor/acceptor layer the number of incident photons. Both aspects can increase the photogenerated current to improve the power conversion efficiency of photovoltaic cells. The OPV device of this embodiment achieves the dual effects of exciton blocking and solar light enhancement simultaneously in a simple way without additional optical design and complicated process. This embodiment has a simple preparation process, low equipment requirements, and is suitable for mass production.

Embodiment two:

This embodiment is basically the same as Embodiment 1, especially in that:

In this embodiment, referring to FIG. 1 , a transparent ITO glass substrate etched into a certain template is selected as the anode, and the thickness of the ITO glass substrate is 150 nm. Use lotion, acetone, deionized water, and isopropanol to ultrasonically clean for 20 minutes in sequence, blow dry with nitrogen, and treat with UV/O ₃ for 15 minutes before use. By vacuum evaporation method, the hole injection layer MoO ₃ is deposited on the ITO glass substrate with a thickness of 10nm, and then the exciton blocking layer BSB-Cz is deposited with a thickness of 8-20nm, and then the donor SubPc is deposited with a thickness of 10nm. 7-20nm and acceptor layer C ₆₀ with a thickness of 30-50nm, then deposit the electron transport layer material Bphen with a thickness of 5-10nm, and then replace the mask plate to evaporate the cathode metal, and evaporate the metal Al as the cathode with a thickness of 100nm .

The absorption and emission spectra of the exciton blocking layer BSB-Cz in this embodiment are shown in Fig. 2 and Fig. 3 respectively. The absorption peak of BSB-Cz is 370nm, and the emission peak is 478nm. The absorption spectra of the donor layer SubPc and the acceptor layer C ₆₀ are shown in FIG. 4 . The blue-green light emitted by BSB-Cz is just in the absorption range of SubPc and C ₆₀ , which additionally enhances the solar light intensity and plays an electron blocking role at the same time.

In this embodiment, also through material matching, the same hole transport layer can simultaneously realize the effect of exciton blocking and enhancing the incident light intensity of the subsequent donor/acceptor layer. It has the characteristics of low cost, simple structure and process, and can be prepared on a flexible substrate. It can be widely used in solar power generation.

The embodiments of the present invention have been described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention of the present invention. The changes, modifications, substitutions, combinations or simplifications should be equivalent replacement methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the concept of the integrated hole transport layer with exciton blocking and solar light sensitization of the present invention The technical principles and inventive concepts of the organic solar cell and its preparation method all belong to the protection scope of the present invention.

Claims (9)

1. An organic solar cell with an integrated hole-transporting layer for exciton blocking and sunlight sensitization, characterized in that: from bottom to top, substrate layer (1), transparent conductive anode layer (2), empty Hole injection layer (3), exciton blocking layer (4), donor layer (5), acceptor layer (6), electron transport layer (7) and electrode cathode layer (8), the donor layer (5) It is made of any material or any several materials in organic solar cell materials with narrow band and strong absorption, and the acceptor layer (6) is made of any material in fullerene or fullerene derivative material Made of one material or any several materials, the thickness of the exciton blocking layer (4) is 5-20nm, and the material of the exciton blocking layer (4) is a wide-bandgap UV absorption and hardly absorbs visible light hole transport material, and the energy level of the exciton blocking layer (4) matches the energy level of the donor layer (5). Preparation of any one process or combination of processes with any mechanism; The material of the exciton blocking layer (4) adopts any material or any several materials in blue fluorescent material, green fluorescent material, blue phosphorescent material and green phosphorescent material, and the blue fluorescent material adopts dark blue dye 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,N'-diphenyl-N,N'-bis(1-naphthylphenyl)-1,1'-biphenyl-4,4'-diamine(<-NPD),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- Any material or any several materials in phenyl-1,3,5-triazine (CC2TA), the green fluorescent material adopts 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-yl) isophthalonitrile (4CzIPN) in any material or any several materials, the blue phosphorescent material adopts iridium bis (4,6-difloroPhenyl-pyridinato-N, C') picolinate (Firpic ), iridium(Ⅲ)bis(4,6-difluorophenylpyridinato)tetrakis(1-pyraZolyl)borate(Fir6), I Any one material or any several materials in ridium (Ⅲ) bis (4,6-difluorophenyl-pyridinato)-5-(pyridine-2-yl)-1H-tetrazolate) (FirN4); the green phosphorescent material adopts fac-tris(2-phenylpyridine)iridium(Ir(ppy) ₃ ), bis(2-phenylpyridine)iridium(acetyl-acetonate)((ppy) ₂ Ir(acac)), tris[3,6-bis(phenyl )-pyridazinato-N ₁ ,C ₂ ']iridium (Ir(BPPya) ₃ ) any one material or any several materials; The material of the donor layer (5) is boron subphthalocyanine chloride (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-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7-tetramethyljulolidyl- Any one material or any several materials in 9-enyl)-4H-pyran (DCJTB). 2. The organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization according to claim 1, characterized in that: the transparent substrate (1) and the transparent conductive anode (2) are composed of The thickness of the substrate is 100-150nm, the thickness of the hole injection layer (3) is 5-10nm, the thickness of the donor layer (5) is 10-25nm, the thickness of the acceptor layer (6) 30-50nm, the thickness of the electron transport layer (7) is 5-10nm, and the thickness of the electrode cathode layer (8) is 80-100nm. 3. According to claim 1 or 2, there is an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization, characterized in that: the material of the substrate layer (1) is rigid glass material, transparent Any one of polymer flexible material or biodegradable flexible material or any composite material of several kinds, wherein the transparent polymer flexible material is polyethylene, polymethyl methacrylate, polycarbonate, polyurethane Any one material or any several materials in formate, polyimide, polyacrylic resin and polyacrylic acid. 4. according to claim 1 and 2 described organic solar cells with exciton blocking and sunlight sensitizing integrated hole transport layer, it is characterized in that: the material of described transparent conductive anode (2) is indium tin oxide ( ITO), conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS), graphene, carbon nanotube, metal element, metal element nanowire, metal alloy nano Any one material or any several materials in wires, metal heterojunction nanowires. 5. The organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization according to claim 1 or 2, characterized in that: the material of the hole injection layer (3) is MoO ₃ , Any one material or any several materials among V ₂ O ₅ , NiO ₂ , WO ₃ . 6. According to claim 1 or 2, there is an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization, characterized in that: the material of the acceptor layer (6) is fullerene or richerene C ₆₀ , C ₇₀ , [6,6]-phenyl C71 butyric acid methyl ester(PC71BM), [6,6]-phenyl C61butyric acid methyl ester(PC61BM), indene-C60 bisadduct(ICBA) in allene derivative materials , poly(9,9-dioctylfluorene-co-benzothiadiazole (F8BT) any one material or any several materials. 7. According to claim 1 and 2, there is an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization, characterized in that: the material of the electron transport layer (7) is graphene, carbon Nanotubes, ZnO, Cs ₂ CO ₃ , 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 oxadiazole compounds, quinoxaline compounds, cyano-containing polymers, other nitrogen-containing heterocyclic compounds, silicone materials, perfluorinated Any one material or any several materials in chemical materials and organoboron materials. 8. According to claim 1 and 2, there is an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization, characterized in that: said electrode cathode layer (8) is Al, Ag, magnesium silver Any one material or any several materials in alloys and lithium aluminum alloys. 9. a method for preparing an organic solar cell with an integrated hole transport layer for exciton blocking and sunlight sensitization according to claim 1, characterized in that, comprising the following steps: 1) Clean the substrate composed of the transparent substrate and the transparent conductive anode, and dry it with dry nitrogen after cleaning; 2) Prepare a hole injection layer on the surface of the transparent conductive anode in step 1) by using spin coating, printing, spray coating or evaporation, and using a hole injection layer material; 3) Using spin coating, printing, spray coating or evaporation, and using a hole transport material, an exciton blocking layer is prepared on the surface of the hole injection layer prepared in the step 2); 4) Using spin coating, printing, spraying or evaporation, and using an organic electron donor layer material, preparing a donor layer on the surface of the exciton blocking layer prepared in the step 3); 5) Using spin coating, printing, spraying or vapor deposition, and using electron acceptor layer materials, preparing an acceptor layer on the surface of the donor layer prepared in the step 4); 6) Using spin coating, printing, spraying or evaporation, and using electron transport layer materials, preparing an electron transport layer on the surface of the acceptor layer prepared in step 5); 7) The mask plate is replaced, and the cathode material is evaporated on the surface of the electron transport layer prepared in the step 6) to form an electrode cathode layer, thereby making each functional layer of the organic solar cell.