CN104795500A - Organic thin-film solar cell using bulk heterojunctions as linking layers and production method of solar cell - Google Patents
Organic thin-film solar cell using bulk heterojunctions as linking layers and production method of solar cell Download PDFInfo
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Abstract
The invention discloses an organic thin-film solar cell using bulk heterojunctions as linking layers and a production method of the solar cell. The solar cell uses a positive structure and sequentially comprises a transparent substrate, a transparent anode electrode, an anode decoration layer, a donor material layer, a first linking layer, a bipolar material layer, a second linking layer, a receptor material layer, an electronic buffer layer and a cathode electrode from bottom to top, wherein the first linking layer is formed by mixing P type materials and bipolar materials, and the second linking layer is formed by mixing bipolar materials and N type materials. The organic thin-film solar cell has the advantages that the P type materials, the N type materials and the bipolar materials are mixed to form the linking layers among the active layers of P type/bipolar/N type structures, light of different wavebands is absorbed, the linking degree of the active layers is increased, device film forming effect is enhanced, device light-generated currents are increased, device light absorption efficiency is increased greatly, and solar cell conversion efficiency is increased.
Description
Technical field
The invention belongs to organic solar batteries field, be specifically related to a kind of based on the organic thin film solar cell and preparation method thereof of bulk heterojunction as active layer connecting layer.
Background technology
Along with the increase year by year of global energy requirements amount, urgent problem is become to effective utilization of regenerative resource.The energy great majority used in the world at present come from the exploitation of fossil energy, comprising oil, and natural gas and coal etc.But these resources are all limited.By contrast, the solar energy taking up an area ball gross energy more than 99% has inexhaustible, the feature such as not to pollute, thus becomes one of green novel energy source of countries in the world scientist's development and utilization.Solar cell is the photovoltaic device converted solar energy into electrical energy, and wherein, the technology of inorganic solar cell is comparatively ripe, and efficiency is far above organic solar batteries.But, the processing technology of inorganic semiconductor material is very complicated, material requirements is harsh, manufacture energy consumption greatly, not easily carries out large area flexible processing, production equipment is expensive, some material has toxicity etc., and these shortcomings constrain further developing of inorganic solar cell.Organic solar batteries with its technique simply, cheap material, the features such as applicability widely, becomes output on a large scale, pollutes less, quality is light, collapsible, progressively move towards leading position.
At present, the biggest problem of organic solar batteries is that its transformation efficiency is low.The highest current transformation efficiency is more than 10%, but the application of price distance business also has certain gap, so the raising transformation efficiency of cheapness is the main target of organic solar batteries research.Low a lot of because have of organic solar batteries transformation efficiency, as photovoltaic material, to absorb luminous energy few, and the exciton produced is easy to compound, the restriction of exciton transfer distance, causes exciton bulk deposition and cancellation.The spectral width that each organic material can absorb is limited, many materials are only responsive to narrow spectral region, and the main method addressed this problem has two kinds: find the wider material of spectral absorption or utilize the multiple material that can absorb different spectral region.The former needs to produce brand-new photovoltaic material, and realize difficulty comparatively large, the latter then can utilize existing material to mate.On general organic solar batteries device, exciton again compound is a problem always, and this problem comes from the transmission range of exciton own, and wanting to address this problem is generally by being mixed to form bulk heterojunction or multiple planar heterojunction.Organic material adulterates mutually by the former, utilizes the feature of bulk heterojunction like this, namely rolls up bi-material contact-making surface, and exciton can transmit and be separated immediately, improves efficiency of transmission; The exciton that the whole device of the latter produces after absorbing light carries out the separation of exciton with regard to not being diffused into that unique heterojunction boundary, also can carry out the separation of exciton, substantially increase the separative efficiency of exciton at other heterojunction boundaries near exciton.
But the solar cell FF that such structure is formed is not still high especially, the very short still transmission of some exciton length less than, the game between active layer thickness and exciton length still exists.If therefore raising exciton transfer efficiency and separative efficiency are research emphasis and the difficult points of solar cell.
Summary of the invention
How the object of the invention provides a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, improves organic solar batteries exciton transfer efficiency and separative efficiency.
Technical scheme of the present invention is: a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, adopt eurymeric structure, be followed successively by transparent substrates, transparent anode electrode, anode modification layer, donor material layer, connecting layer one, bipolar materials layer, connecting layer two, receptor material layer, electron buffer layer and cathode electrode from top to bottom, connecting layer one is mixed to form mutually by P-type material and bipolar materials, and connecting layer two is mixed to form mutually by bipolar materials and n type material.
Further, in the present invention, P-type material is: poly-(3-hexyl thiophene), poly-(2-methoxyl group-5-(2-ethyl hexyl oxy)-1,4-phenylene ethylene), poly-[[9-(1-octyl group nonyl)-9H-carbazole-2,7-bis-base]-2,5-thiophene two base-2,1,3-diazosulfide-4,7-bis-base-2,5-thiophene two base], polystyrene support series material, polythiophene series material or a kind of based on aromatic ring and in the donor material of thiadiazoles group or their mixing, preferably adopt TTPA material in the present invention.
Further, in the present invention, n type material is: fullerene derivate, BBL, PTPTB or containing a kind of in pyrene imide polymer or their mixing, preferably adopt C in the present invention
60material.
Further, in the present invention, bipolar materials is phthalocyanine-like compound, adopts sub-phthalocyanine in the present invention.
Further, in the present invention, connecting layer one is mixed to form by TTPA and SubPc, and connecting layer two is by SubPc and C
60be mixed to form.
Further, in the present invention, the thickness of donor material layer is X nm; In connecting layer one, the Mixing ratio by weight example of P-type material and bipolar materials is 1:4, and its thickness is (90-3X)/2nm; The thickness of bipolar materials layer is X nm; In connecting layer two, the Mixing ratio by weight example of bipolar materials and n type material is 1:4, and its thickness is (90-3X)/2nm; The thickness of n type material is X nm, and wherein the value of X is 20 ~ 30.
Further, in the present invention, described anode modification layer is organic conductive polymer film or metal-oxide film, wherein organic conductive polymer film is PEDOT ︰ PSS or PANI class organic conductive polymer film, metal-oxide film is Electrochromic Molybdenum Oxide Coatings or nickel oxide film, adopts PEDOT ︰ PSS in the present invention.
Further, in the present invention, transparent substrates is glass or flexible substrate or sheet metal; Transparent anode electrode is metal-oxide film; Cathode electrode is a kind of in lithium, magnesium, calcium, strontium, aluminium or indium or the alloy by them, preferably adopts Ag as cathode electrode in the present invention.
The invention provides a kind of based on the preparation method of bulk heterojunction as the organic thin film solar cell of active layer connecting layer, it comprises the following steps:
1. wash the substrate be made up of transparent substrates and transparent conductive anode ITO, then dry up with nitrogen;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode modification layer solution, and formed film is toasted, prepare anode pole decorative layer;
3. on anode modification layer, preparation forms donor material layer;
4. in donor material layer, preparation forms connecting layer one;
5. on connecting layer one, preparation forms bipolar materials layer;
6. on bipolar materials layer, preparation forms connecting layer two;
7. on connecting layer two, preparation forms receptor material layer;
8. on receptor material layer, preparation forms electron buffer layer;
9. in electron buffer layer, preparation forms negative electrode.
Further, the described step temperature that 2. middle film toasts is 120 ~ 150 DEG C, and the time is 5 ~ 60min.
Further, transparent anode electrode and cathode electrode are by the chemical vapour deposition (CVD) of vacuum thermal evaporation, magnetron sputtering, plasma enhancing, silk screen printing or a kind of method preparation in printing.
Further, connecting layer one, connecting layer two and electron buffer layer are by the chemical vapour deposition (CVD) of plasma enhancing, thermal oxidation, spin coating, vacuum evaporation, a kind of method preparation of dripping in film, impression, printing or gas blowout.
In the present invention, connecting layer is adulterated between two by three kinds of material of main parts and is formed, three kinds of materials are respectively P-type material, n type material and bipolar materials, due to the polarities match between P, N and bipolarity, two kinds of heterojunction boundaries can be formed, P type/bipolarity and bipolarity/N-type respectively, two kinds of heterojunction boundaries.Then by P-type material and bipolar materials, bipolar materials and n type material are mixed to form connecting layer mutually, improve further " quantity " of two kinds of heterojunction boundaries, thus improve the separative efficiency of exciton.Meanwhile, the absorption spectrum of three kinds of materials is not overlapping mutually, and the light absorption of device is increased.Because there has been connecting layer, charge carrier has increased in the transmittability at interface.
On P type/bipolarity/N-type cascaded structure basis, between each active layer, with the addition of connecting layer, be conducive to the transmission of film forming between active layer and electron hole.
Compared with prior art: tool of the present invention has the following advantages:
1. improve the absorption region of spectrum.
2. improve the production rate of charge carrier.
3. add the separating interface of exciton, thus improve the utilization ratio of exciton.
4. improve the efficiency of transmission of charge carrier.
5. add cell conversion efficiency.
Accompanying drawing explanation
Fig. 1 is that the present invention is a kind of based on the structural representation of bulk heterojunction as the organic thin film solar cell of active layer connecting layer;
Fig. 2 is that the present invention is a kind of based on the organic thin film solar cell active layer inner exciton dissociation of bulk heterojunction as active layer connecting layer and the schematic diagram of carrier mobility;
Fig. 3 is that the present invention is a kind of based on the J-V curve chart of bulk heterojunction as the organic thin film solar cell certain embodiments of active layer connecting layer;
Fig. 4 is that the present invention is a kind of based on the spectrogram of bulk heterojunction as each material of organic thin film solar cell of active layer connecting layer.
Embodiment
Technical scheme of the present invention is to provide a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, as shown in Figure 1, device architecture comprises transparent substrates 1, transparent anode electrode 2, anode modification layer 3, donor material layer 4, connecting layer 1, bipolar materials layer 6, connecting layer 27, receptor material layer 8, electron buffer layer 9, cathode electrode 10.
Transparent substrates 1 in the present invention is the support of whole device, and at least within the scope of visible frequency, there is high transmitance, have the effect of certain anti-steam and oxygen infiltration, the evenness on surface is higher, and it can be glass, flexible substrate, sheet metal or tinsel.
The material of the transparent anode electrode 2 in the present invention is inorganic, metal oxide (as tin indium oxide ITO, zinc oxide ZnO etc.).Material requirements at least has high transmitance within the scope of visible frequency, and the conductivity of material is high, and has higher work function.
Anode modification layer 3 in the present invention is organic conductive polymer film PEDOT:PSS.
P-type material in the present invention is TTPA, and that bipolar materials layer adopts is SubPc, and that receptor material layer adopts is C
60.
Connecting layer in the present invention is respectively P-type material+bipolar materials, bipolar materials+n type material, P-type material and bipolar materials have identical HOMO energy level, and can heterojunction be formed, bipolar materials and n type material also can form heterojunction simultaneously, meeting this material required is P-type material: TTPA, bipolar materials: SubPc, n type material: C
60.
Electron buffer layer 9 in the present invention is metal organic complexes, pyridines, o-phenanthroline class, one in oxadiazole class or glyoxaline compound material, wherein metal organic complex comprises oxine aluminium or two (2-methyl-8-quino)-4-(phenylphenol) aluminium, pyridine compounds and their comprises three [2, 4, 6-trimethyl-3-(pyridine-3-yl) phenyl]-borine, o-phenanthroline compounds comprises 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthrolene or 4, 7-biphenyl-1, 10-phenanthrolene, oxadiazole electron transport material is 2-(4-diphenyl)-5-(4-2-methyl-2-phenylpropane base)-1, 3, 4-oxadiazole or 1, 3-bis-[(4-tertiary amine-butyl phenyl)-1, 3, 4-diazo acid-5-yl] benzene, imidazoles electron transport material is 1, 3, 5-tri-(N-Phenyl-benzoimidazol-2) benzene etc.
Cathode electrode 10 in the present invention can be lithium, magnesium, calcium, strontium, aluminium, indium or their alloys of being combined to form.Material requirements has good conductivity, and the work function of material is low.
In the present invention, the temperature of film baking is 120 ~ 150 DEG C, and the time is 5 ~ 60min.
In the present invention, transparent anode electrode and cathode electrode are by the chemical vapour deposition (CVD) of vacuum thermal evaporation, magnetron sputtering, plasma enhancing, silk screen printing or a kind of method preparation in printing.
In the present invention, connecting layer one, connecting layer two and electron buffer layer are by the chemical vapour deposition (CVD) of plasma enhancing, thermal oxidation, spin coating, vacuum evaporation, a kind of method preparation of dripping in film, impression, printing or gas blowout.
Here is the specific embodiment of this example:
Embodiment 1:
Device architecture as shown in Figure 1.The material of device layers and thickness and doping ratio are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 30nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 0nm; Bipolar materials layer is SubPc, and thickness is 30nm; Connecting layer two is SubPc:C
60=1:4, thickness is 0nm; Receptor material layer is C
60, thickness is 30nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.
Its preparation method is as follows:
1. washing agent, acetone soln, deionized water and ethanolic solution ultrasonic cleaning are used to the glass substrate having sputtered transparent anode electrode ITO, dry up with drying nitrogen after cleaning;
2. above-mentioned ITO substrate is moved into vacuum chamber, under the environment of the air pressure of 25Pa, oxygen and argon gas, carry out plasma treatment 5 minutes to ito glass, sputtering power is 20W, cools 15 minutes afterwards.
3. the substrate after above-mentioned process is placed in sol evenning machine, spin-on organic materials PEDOT:PSS, utilizing rotating speed and spin-coating time to control thickness is 30nm.Then at 140 DEG C dry 10 minutes.
4. the substrate after above-mentioned process is placed in vacuum degree and is greater than 1 × 10
-5in organic chamber vaporization chamber of Pa, start the evaporation carrying out organic film.Evaporation TTPA, evaporation rate is 0.1nm/s, and thickness is 30nm; Connecting layer five is according to the speed evaporation of TTPA:SubPc=1:4, and thickness is 0nm; The evaporation rate 0.025nm/s of SubPc, thickness is 30nm; Connecting layer 7 is according to SubPc and C
60the speed evaporation of=1:4, thickness is 0nm; C
60evaporation rate be 0.1nm/s, thickness is 30nm; Evaporation rate and thickness are monitored by the crystal oscillator film thickness gauge be arranged near substrate.
6. above-mentioned substrate is placed in vacuum degree and is greater than 1 × 10
-5in organic chamber vaporization chamber of Pa, evaporation electron transport layer materials Bphen, thickness is 5nm, and speed is 0.1nm/s, and evaporation rate and thickness are monitored by the crystal oscillator film thickness gauge be arranged near substrate.
7. the preparation of laggard row metal electrode has been prepared at above-mentioned organic film.Evaporation air pressure is 3 × 10
-3pa, evaporation rate is l nm/s, and electrode material is Ag, and thickness is 130nm, and evaporation rate and thickness are monitored by the crystal oscillator film thickness gauge be arranged near substrate
Embodiment 2:
Device architecture as shown in Figure 1.The material of device layers and thickness and mixed proportion are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 29nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 1.5nm; Bipolar materials layer is SubPc, and thickness is 29nm; Connecting layer two is SubPc:C
60=1:4, thickness is 1.5nm; Receptor material layer is C
60, thickness is 29nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.Preparation flow and example 1 substantially similar.
Embodiment 3:
Device architecture as shown in Figure 1.The material of device layers and thickness and mixed proportion are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 28nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 3nm; Bipolar materials layer is SubPc, and thickness is 28nm; Connecting layer two is SubPc:C
60=1:4, thickness is 3nm; Receptor material layer is C
60, thickness is 28nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.Preparation flow and example 1 similar.
Embodiment 4
Device architecture as shown in Figure 1.The material of device layers and thickness and mixed proportion are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 27nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 4.5nm; Bipolar materials layer is SubPc, and thickness is 27nm; Connecting layer two is SubPc:C
60=1:4, thickness is 4.5nm; Receptor material layer is C
60, thickness is 27nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.Preparation flow and example 1 similar.
Embodiment 5
Device architecture as shown in Figure 1.The material of device layers and thickness and mixed proportion are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 26nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 6nm; Bipolar materials layer is SubPc, and thickness is 26nm; Connecting layer two is SubPc:C
60=1:4, thickness is 6nm; Receptor material layer is C
60, thickness is 26nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.Preparation flow and example 1 similar.
Embodiment 6:
Device architecture as shown in Figure 1.The material of device layers and thickness and mixed proportion are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 25nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 7.5nm; Bipolar materials layer is SubPc, and thickness is 25nm; Connecting layer two is SubPc:C
60=1:4, thickness is 7.5nm; Receptor material layer is C
60, thickness is 25nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.Preparation flow and example 1 similar.
Embodiment 7:
Device architecture as shown in Figure 1.The material of device layers and thickness and doping ratio are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 24nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 9nm; Bipolar materials layer is SubPc, and thickness is 24nm; Connecting layer two is SubPc:C
60=1:4, thickness is 9nm; Receptor material layer is C
60, thickness is 24nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.
Embodiment 8:
Device architecture as shown in Figure 1.The material of device layers and thickness and doping ratio are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 23nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 10.5nm; Bipolar materials layer is SubPc, and thickness is 23nm; Connecting layer two is SubPc:C
60=1:4, thickness is 10.5nm; Receptor material layer is C
60, thickness is 23nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.
Embodiment 9:
Device architecture as shown in Figure 1.The material of device layers and thickness and doping ratio are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 22nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 12nm; Bipolar materials layer is SubPc, and thickness is 22nm; Connecting layer two is SubPc:C
60=1:4, thickness is 12nm; Receptor material layer is C
60, thickness is 22nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.
Embodiment 10:
Device architecture as shown in Figure 1.The material of device layers and thickness and doping ratio are: transparent substrates is glass, and transparent anode electrode is ITO, and thickness is 180nm; Anode modification layer is PEDOT:PSS, and thickness is 30nm; Donor material layer is TTPA, and thickness is 21nm; Connecting layer one is TTPA:SubPc=1:4, and thickness is 13.5nm; Bipolar materials layer is SubPc, and thickness is 21nm; Connecting layer two is SubPc:C
60=1:4, thickness is 13.5nm; Receptor material layer is C
60, thickness is 21nm; Electron buffer layer is Bphen, and thickness is 5nm; Cathode electrode is Ag, and thickness is 130nm.
What in Fig. 3, efficiency was minimum is TTPA, SubPc bis-Give body structure, open circuit voltage, and short circuit current, FF is minimum.After the connecting layer of interpolation two mixture heterojunction, open circuit voltage, short circuit current has had significant raising, and it is most effective when the mixed layer of TTPA, SubPc mixed layer and SubPc, C60 is all 1:4, demonstrate the lifting of effect for efficiency of this connecting layer, the absorption spectrum peak value of three materials separately at visible ray spectrally, does not have overlap, adds absorption efficiency.
The above embodiment only have expressed the embodiment of the application, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the application's protection range.It should be pointed out that for the person of ordinary skill of the art, under the prerequisite not departing from technical scheme design, can also make some distortion and improvement, these all belong to the protection range of the application.
Claims (10)
1. one kind based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, it is characterized in that, adopt eurymeric structure, be followed successively by transparent substrates, transparent anode electrode, anode modification layer, donor material layer, connecting layer one, bipolar materials layer, connecting layer two, receptor material layer, electron buffer layer and cathode electrode from top to bottom, connecting layer one is mixed to form mutually by P-type material and bipolar materials, and connecting layer two is mixed to form mutually by bipolar materials and n type material.
2. according to claim 1 a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, it is characterized in that, P-type material is: poly-(3-hexyl thiophene), poly-(2-methoxyl group-5-(2-ethyl hexyl oxy)-1, 4-phenylene ethylene), poly-[[9-(1-octyl group nonyl)-9H-carbazole-2, 7-bis-base]-2, 5-thiophene two base-2, 1, 3-diazosulfide-4, 7-bis-base-2, 5-thiophene two base], polystyrene support series material, polythiophene series material or a kind of based on aromatic ring and in the donor material of thiadiazoles group or their mixing.
3. according to claim 1 a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, it is characterized in that, n type material is: fullerene derivate, BBL, PTPTB or containing a kind of in pyrene imide polymer or their mixing.
4. according to claim 1ly a kind ofly to it is characterized in that based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, bipolar materials is sub-phthalocyanine.
5. according to claim 1ly a kind ofly to it is characterized in that based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, connecting layer one is mixed to form by TTPA and SubPc, and connecting layer two is by SubPc and C
60be mixed to form.
6. according to claim 1ly a kind ofly to it is characterized in that based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, the thickness of donor material layer is X nm; In connecting layer one, the Mixing ratio by weight example of P-type material and bipolar materials is 1:4, and its thickness is (90-3X)/2nm; The thickness of bipolar materials layer is X nm; In connecting layer two, the Mixing ratio by weight example of bipolar materials and n type material is 1:4, and its thickness is (90-3X)/2nm; The thickness of n type material is X nm, and wherein the value of X is 20 ~ 30.
7. according to claim 1 a kind of based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, it is characterized in that, anode modification layer is organic conductive polymer film or metal-oxide film, wherein organic conductive polymer film is PEDOT ︰ PSS or PANI class organic conductive polymer film, and metal-oxide film is Electrochromic Molybdenum Oxide Coatings or nickel oxide film.
8. according to claim 1ly a kind ofly to it is characterized in that based on the organic thin film solar cell of bulk heterojunction as active layer connecting layer, transparent substrates is glass or flexible substrate or sheet metal; Transparent anode electrode is metal-oxide film; Cathode electrode is a kind of in lithium, magnesium, calcium, strontium, aluminium or indium or the alloy by them.
9. a kind of based on the preparation method of bulk heterojunction as the organic thin film solar cell of active layer connecting layer according to any one of claim 1-8, it is characterized in that, it comprises the following steps:
1. wash the substrate be made up of transparent substrates and transparent conductive anode ITO, then dry up with nitrogen;
2. at transparent conductive anode ITO surface rotary coating, printing or spraying anode modification layer solution, and formed film is toasted, prepare anode pole decorative layer;
3. on anode modification layer, preparation forms donor material layer;
4. in donor material layer, preparation forms connecting layer one;
5. on connecting layer one, preparation forms bipolar materials layer;
6. on bipolar materials layer, preparation forms connecting layer two;
7. on connecting layer two, preparation forms receptor material layer;
8. on receptor material layer, preparation forms electron buffer layer;
9. in electron buffer layer, preparation forms negative electrode.
10. according to claim 1 a kind of based on the preparation method of bulk heterojunction as the organic thin film solar cell of active layer connecting layer, it is characterized in that, the described step temperature that 2. middle film toasts is 120 ~ 150 DEG C, time is 5 ~ 60min, transparent anode electrode and cathode electrode pass through vacuum thermal evaporation, magnetron sputtering, the chemical vapour deposition (CVD) of plasma enhancing, silk screen printing or a kind of method preparation in printing, connecting layer one, connecting layer two and electron buffer layer are by the chemical vapour deposition (CVD) of plasma enhancing, thermal oxidation, spin coating, vacuum evaporation, drip film, impression, a kind of method preparation in printing or gas blowout.
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