CN106816533A - A kind of phthalocyanine derivates film as cathode buffer layer inverse organic solar cell and preparation method thereof - Google Patents

A kind of phthalocyanine derivates film as cathode buffer layer inverse organic solar cell and preparation method thereof Download PDF

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CN106816533A
CN106816533A CN201710136875.8A CN201710136875A CN106816533A CN 106816533 A CN106816533 A CN 106816533A CN 201710136875 A CN201710136875 A CN 201710136875A CN 106816533 A CN106816533 A CN 106816533A
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buffer layer
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organic solar
cathode buffer
phthalocyanine derivates
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CN106816533B (en
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张宏梅
郑爽
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Nanjing Post and Telecommunication University
Nanjing University of Posts and Telecommunications
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Nanjing Post and Telecommunication University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/42Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture
    • H01L51/4253Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for sensing infra-red radiation, light, electro-magnetic radiation of shorter wavelength or corpuscular radiation and adapted for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation using organic materials as the active part, or using a combination of organic materials with other material as the active part; Multistep processes for their manufacture comprising bulk hetero-junctions, e.g. interpenetrating networks
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0026Thermal treatment of the active layer, e.g. annealing
    • HELECTRICITY
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0026Thermal treatment of the active layer, e.g. annealing
    • H01L51/0028Thermal treatment in the presence of solvent vapors, e.g. solvent annealing
    • HELECTRICITY
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0034Organic polymers or oligomers
    • H01L51/0035Organic polymers or oligomers comprising aromatic, heteroaromatic, or arrylic chains, e.g. polyaniline, polyphenylene, polyphenylene vinylene
    • H01L51/0036Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0045Carbon containing materials, e.g. carbon nanotubes, fullerenes
    • H01L51/0046Fullerenes, e.g. C60, C70
    • H01L51/0047Fullerenes, e.g. C60, C70 comprising substituents, e.g. PCBM
    • HELECTRICITY
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    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0032Selection of organic semiconducting materials, e.g. organic light sensitive or organic light emitting materials
    • H01L51/0077Coordination compounds, e.g. porphyrin
    • H01L51/0078Phthalocyanine
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to a kind of phthalocyanine derivates film as cathode buffer layer inverse organic solar cell and preparation method thereof.It is annealed by solvent vapo(u)r or transfer chamber air-flow makes annealing treatment the phthalocyanine derivates ZnPc (OC of the crystalline order degree that can efficiently control cushioning layer material phthalocyanine derivates, the roughness of reduction film surface, and ionic8H17OPyCH3I)8Synthetic method is simple, and alcohol-soluble is very good, is environmentally friendly nontoxic ideal cathodes boundary material.Acidic hole transmission material PEDOT is not included in inverted structure device of the invention:PSS and low workfunction metal electrode, so the efficiency of device is significantly improved with stability.Compared with research in the past, the inventive method is novel, and preparation process is simple is cheap, is the effective ways for improving solar cell properties.The organic solar batteries device prepared by the present invention remains to keep after 500 hours more than 80% efficiency, hence it is evident that higher than traditional devices.

Description

A kind of phthalocyanine derivates film as cathode buffer layer inverse organic solar cell And preparation method thereof
Technical field
The present invention relates to a kind of inverted structure organic solar batteries, and in particular to a kind of phthalocyanine derivates ZnPc (OC8H17OPyCH3I)8Film belongs to solar-electricity as the inverse organic solar cell and preparation method thereof of cathode buffer layer Pool technology field.
Background technology
On the premise of World Economics develops on a large scale, energy shortage has become World Economics and can hold with problem of environmental pollution The bottleneck problem of supervention exhibition.Solar energy is because its is pollution-free, reserves are big, renewable, distribution is wide, be easy to the advantages such as collection to obtain The extensive concern of people, is the ideal candidate of people's solution energy crisis and environmental pollution, is had in global energy strategy Very important status.
Polymer solar battery is due to its materials synthesis diversity, light weight, low cost, it is easy to the volume to volume of large area Prepare, can directly be prepared into the extensive concern that many advantages such as flexible device have been obtained for industry people.However, organic photoelectric The raising of device performance can be realized by the optimization of device, including film morphology control(Adv. Funct. Mater., 15(2005)1617–1622), light regulation and control(Adv. Mater., 23(2011)3465–3470), modifying interface(J. Mater. Chem.20(2010)2 575–2598).Recently, there has been the boundary that notice is transferred to many workers organic electro-optic device Come in the technique of face.Interfacial characteristics is considered as one of key factor that influence device performance is improved.Can by active layer with Suitable boundary layer is simply inserted between metal electrode to significantly improve device performance.It is selected now with many interlayer materials Make the boundary layer of male or female.Including transition metal oxide, conjugated polymer electrolyte, interface coupling pole injection material etc..
At present, on the one hand its stability stills need further raising, another aspect organic solar to solar cell device Battery material toxicity is larger, and environmental pollution is serious, is not suitable for commercialization, and this runs in the opposite direction with the state basic policy of current China.Therefore Urgent need finds a kind of materials application not polluted to environment in solar cells, improves solar cell properties and stability And pollution problem of the organic solar batteries to environment is reduced, this is also the trend of the future development of field of batteries.
The content of the invention
Technical problem:What the present invention put forward aiming above mentioned problem, present invention firstly provides a kind of phthalocyanine derivates Film as cathode buffer layer inverse organic solar cell and preparation method thereof, the inverse organic solar cell is with solvent Steam annealing or transfer chamber air-flow method for annealing treatment ZnPc (OC8H17OPyCH3I)8Film improve solar cell properties and Stability.
Technical scheme:The purpose of the present invention is achieved through the following technical solutions:A kind of phthalocyanine derivates film is used as negative electrode The inverse organic solar cell of cushion, the structure of the inverse organic solar cell is respectively from bottom to top:Transparent lining Bottom, transparent cathode, cathode buffer layer, light-absorption layer, hole transmission layer and metal anode.
In the light-absorption layer, electron donor material is poly- 3- base thiophene P3HT, and electron acceptor material is [6,6]-phenyl C61- methyl butyrate PC61BM, its poly- 3- base thiophene P3HT and [6,6]-phenyl C61- methyl butyrate PC61The mass ratio of BM is 1:1。
The hole transport layer material is molybdenum oxide MoO3
The material of the metal anode is the one kind in Al, Ag and Au.
The material of the transparent cathode is tin indium oxide ITO.
The material of the transparent substrates is clear glass.
A kind of phthalocyanine derivates film as the inverse organic solar cell of cathode buffer layer preparation method, its preparation Method is comprised the following steps:
1)Transparent cathode and transparent substrates use ITO electro-conductive glass, will etch ITO electro-conductive glass nitrogen that is good and cleaning up Dry up and carry out the ultraviolet and ozone UV-ozone treatment of 15min;
2)The preparation of cathode buffer layer:Spin coating ZnPc (the OC on ITO electro-conductive glass8H17OPyCH3I)8Solution, its spin coating process For first slow-speed of revolution 700r/min rotates 10s, rear rotating speed 3000r/min rotations 60s high, buffer layer thin film is formed, then moved back Fire treatment;The annealing anneal in the environment full of alcohol vapour 20min to be placed the substrates in, or substrate is placed In the small transfer chamber of Braun glove box, transfer chamber air-flow is carried out to device by the inert gas flow circulated in small transfer chamber and is moved back Fiery 20min;
3)The preparation of light-absorption layer:Full of N2Glove box in, with the rotating speed of 800rpm by P3HT:PC61BM solution is spun to the moon On the cushion of pole, spin-coating time is 60s, carried out again after then being dried naturally under room temperature condition 1 hour 120 DEG C annealing 20 minutes at Reason, forms light-absorption layer;
4)The preparation of hole transmission layer:Hole mobile material molybdenum oxide is deposited with light-absorption layer using vacuum evaporation equipment;Evaporation Speed be 0.1/s ~ 0.5/s, its evaporation air pressure environment be less than 3 × 10-4Pa;
5)The preparation of metal anode:Using vacuum evaporation equipment on hole transmission layer evaporation metal, formed metal anode, metal The thickness of anode is 80nm ~ 120nm, and evaporation rate is 5/s ~ 8/s, and the air pressure environment of its evaporation is less than 3 × 10-4 Pa。
The P3HT:PC61BM solution is prepared by the following method:By poly- 3- base thiophene P3HT and [6,6]-phenyl C61- methyl butyrate PC61BM in mass ratio 1:1 is dissolved in dichlorobenzene solution, makes the solution of 17mg/ml concentration, mixed Solution uniform stirring 12 hours at a temperature of 60 DEG C.
ZnPc (the OC8H17OPyCH3I)8Solution is prepared by the following method:By ZnPc (OC8H17OPyCH3I)8 It is dissolved in alcohol solvent, makes the solution of 0.8mg/ml concentration, mixed solution stands at normal temperatures.
Beneficial effect:
(1), present invention firstly provides using solvent vapo(u)r anneal and transfer chamber air-flow anneal two methods process be inverted it is organic too Cathode buffer layer ZnPc (the OC of positive energy battery8H17OPyCH3I)8, enrich the method for improving solar cell properties.
(2), ZnPc (the OC that use of the present invention8H17OPyCH3I)8Material, alcohol-soluble is good, nontoxic, synthetic method letter It is single, there is no any pollution to environment.
(3), the use ZnPc (OC that use of the present invention8H17OPyCH3I)8Material does inverse organic solar cell negative electrode buffering Rotating fields are more novel, preparation process is simple, are adapted to large area production.
(4), the present invention process ZnPc (OC using annealing method8H17OPyCH3I)8Material does cathode buffer layer, effectively controls The crystalline order degree of material, reduces the roughness of buffer-layer surface, cushion is combined with active layer more closely, improves boundary The efficiency of transmission of electric charge at face, the final whole efficiency for improving device.
(5), the present invention process ZnPc (OC using annealing method8H17OPyCH3I)8Material does cathode buffer layer preparation inversion to be had Machine solar cell, improves the incident photoelectron conversion efficiency of device, and the absorption to light.
(6), the present invention process ZnPc (OC using annealing method8H17OPyCH3I)8Material does cathode buffer layer modification inversion to be had Machine solar cell, does not include perishable and hygroscopic hole mobile material PEDOT in inverted structure device:PSS and low Workfunction metal electrode, so as to effectively improve the stability of organic solar batteries.
(7), the present invention use Al as metal anode, it is with low cost, it is environmentally safe.
(8), the packaged type that uses of the present invention using first smearing epoxy resin, then with UV illumination 15 minutes.It is this Not only operating process is simple for packaged type, and can reach good packaging effect.
Brief description of the drawings
Fig. 1 is device of the prepared phthalocyanine derivates film of the present invention as the inverse organic solar cell of cathode buffer layer Structure chart.
Fig. 2 is the J-V curve maps of inverse organic solar cell device obtained in embodiment 1-3.
Fig. 3 is the IPCE performance plots of inverse organic solar cell obtained in embodiment 1-3.
Fig. 4 is the P3HT in inverse organic solar cell obtained in embodiment 1-3:The abosrption spectrogram of PCBM films.
Fig. 5 is the atomic force exterior view of the cathode buffer layer in inverse organic solar cell obtained in embodiment 1-3; (a)Cushion without annealing,(b)Cushion is annealed through transfer chamber air-flow,(c)Cushion is annealed through solvent vapo(u)r.
Fig. 6 is the traditional standard part that inverse organic solar cell device obtained in case study on implementation 2 and embodiment 5 are provided Stability test curve map.
Fig. 7 is two groups of inverse organic solar cell devices that cathode buffer layer is done with Tempo obtained in case study on implementation 4 J-V curve maps.
Specific embodiment
Embodiment 1
To etch and cleaned ITO electro-conductive glass is successively with washing lotion solution, deionized water, acetone, each twice ultrasound of ethanol 15min.By P3HT and PC61BM in mass ratio 1:1 is dissolved in dichlorobenzene solution, the solution of 17mg/ml concentration is made, after mixing Solution at a temperature of 60 DEG C uniform stirring 12 hours, it is stand-by.ZnPc(OC8H17OPyCH3I)8Material is dissolved in alcohol solvent (concentration is 0.8mg/ml).Cleaned ITO electro-conductive glass is dried up and UV15min with nitrogen.Then the spin coating ZnPc on ITO (OC8H17OPyCH3I)8Solution.Its process is first slow-speed of revolution 700r/min rotations 10s, and rear rotating speed 3000r/min high rotates 60s, Form cathode buffer layer.Then the substrate that will be deposited with is sent in the high-quality hand behaviour's case full of N2, with the rotating speed of 800rpm The P3HT that will be stirred:PCBM mixed solutions are spun on cathode buffer layer, and spin-coating time is 60s, under room temperature condition certainly afterwards So dry 1 hour, then carry out 120 DEG C and make annealing treatment 20 minutes, form light-absorption layer.When the air pressure environment of evaporation is less than 3 × 10-4 During Pa, begin to use vacuum evaporation equipment that hole mobile material MoO is deposited with light-absorption layer3, form hole transmission layer.Hole passes The thickness of defeated layer is 8nm, and the speed of evaporation is 0.1/s ~ 0.5/s.And then with 5/s ~ 8 on hole transmission layer The speed of/s is deposited with the aluminium electrode of 100nm thickness, and the air pressure environment of its evaporation is less than 3 × 10-4Pa.Can obtain with ZnPc (OC8H17OPyCH3I)8Do the inverse organic solar cell of cathode buffer layer.Its device architecture is as shown in figure 1, in room temperature environment Under, survey the J-V curves of device.Its device performance is PCE 2.14%, Voc 0.579V, Jsc 8.12mA/cm2, FF 0.45, such as Shown in Fig. 2.ZnPc(OC8H17OPyCH3I)8Spectral response wave-length coverage as the device of cathode buffer layer is as shown in Figure 3;Have Active layer is 60% to the absorptivity of light, as shown in Figure 4;ITO surfaces are by ZnPc (OC8H17OPyCH3I)8Film modified rear roughness It is 1.24nm, as shown in Figure 5 a.ZnPc(OC8H17OPyCH3I)8Alcohol-soluble it is very good, it is environmentally friendly nontoxic, be reason The cathode interface material thought.But by ZnPc (OC8H17OPyCH3I)8Effect is not when material is directly used in the device of inverted structure It is highly desirable, the Film roughness for being spin-coated on ITO surfaces is higher, is contacted with active layer not closely, is unfavorable for forming good Europe Nurse is contacted, and is hindered the transmission of electronics and is collected.
Embodiment 2
Inverse organic solar cell is prepared using method same as Example 1, it is this implementation with the difference of embodiment 1 Example spin coating ZnPc (OC on ITO8H17OPyCH3I)8After solution.Place the substrates in annealing in the environment full of alcohol vapour 20min, forms cathode buffer layer.Obtain with ZnPc (OC8H17OPyCH3I)8The high stability inversion for doing cathode buffer layer is organic too Positive energy battery.Its device architecture is shown in Fig. 1, under room temperature environment, surveys the J-V curves of device.Solvent vapo(u)r is moved back as can be seen from Figure 2 Influence of the fire to organic solar batteries performance, compared with the device of unannealed treatment, device performance is bright after alcohol vapour treatment Aobvious to improve, its device performance has reached PCE 3.76%, Voc 0.579V, Jsc 10.71mA/cm2,FF 0.61.Can be with from Fig. 3 Find out that the spectral response wave-length coverage of the device after solvent anneal is substantially carried compared with without the device of annealing Height, illustrates that the change of the film morphology after solvent anneal treatment is conducive to photoelectronic conversion.From fig. 4, it can be seen that with do not move back The device of fire is compared, and the device after solvent anneal treatment absorbs and is remarkably reinforced, and as a result the result with IPCE is consistent, and this is also device The reason for part current density is improved.Surface roughness 1.02nm, such as Fig. 5 c after solvent vapo(u)r annealing cushion.This because It is that cathode buffer layer ZnPc (OC are made annealing treatment by alcohol vapour8H17OPyCH3I)8Film controls the crystallization of cushioning layer material Process, makes its crystalline growth into degree of order film higher, makes surface finer and close, and more smooth, surface roughness is further reduced, Contacted with active layer more closely beneficial to the transmission of electronics, improve the incident photoelectron conversion efficiency of device, and the absorption to light. The stability of organic solar batteries is greatly improved after being processed through alcohol vapour annealing process, while also improving electricity Pond efficiency.
Embodiment 3
Inverse organic solar cell is prepared using method same as Example 1, it is this implementation with the difference of embodiment 1 Example spin coating ZnPc (OC on ITO8H17OPyCH3I)8After solution.In placing the substrates in the small transfer chamber of Braun glove box, Transfer chamber air-flow annealing 20min is carried out to device by the inert gas flow circulated in small transfer chamber, cathode buffer layer is formed.Obtain With ZnPc (OC8H17OPyCH3I)8Do the high stability inverse organic solar cell of cathode buffer layer.Under room temperature environment, survey The J-V curves of device(See Fig. 2).Influence of the transfer chamber air-flow annealing to organic solar batteries performance as can be seen from Figure 2, with The device of unannealed treatment is significantly improved compared to device performance after excessive cabin air-flow annealing, and its device performance has reached PCE 3.69%,Voc 0.579V,Jsc 10.46mA/cm2,FF 0.61.As can be seen from Figure 3 with the device without annealing Compare, the spectral response wave-length coverage of the device after air-flow annealing is improved significantly, illustrate thin after air-flow annealing The change of film pattern is conducive to photoelectronic conversion.From fig. 4, it can be seen that compared with unannealed device, air-flow annealing Device afterwards absorbs and is remarkably reinforced, and as a result the result with IPCE is consistent, and this is also the reason for device current density is improved. Surface roughness 1.08nm after air-flow annealing cushion, as shown in Figure 5 b.Because being made annealing treatment with transfer chamber air-flow Cathode buffer layer ZnPc (OC8H17OPyCH3I)8Film controls the crystallization process of cushioning layer material, makes its crystalline growth into orderly Degree film higher, makes surface finer and close, more smooth, and surface roughness is further reduced and contacted with active layer more closely beneficial to electricity The transmission of son, improves the incident photoelectron conversion efficiency of device, and the absorption to light.Processed through transfer chamber air-flow annealing process The stability of organic solar batteries is greatly improved afterwards, while also improving battery efficiency.
Embodiment 4
To etch and cleaned ITO electro-conductive glass is successively with washing lotion solution, deionized water, acetone, each twice ultrasound of ethanol 15min.By P3HT and PC61BM in mass ratio 1:1 is dissolved in dichlorobenzene solution, the solution of 17mg/ml concentration is made, after mixing Solution at a temperature of 60 DEG C uniform stirring 12 hours, it is stand-by.Tetramethyl piperidine Tempo (C9H18NO) to be dissolved in acetone molten for material In agent (concentration is 5mg/ml).Cleaned ITO electro-conductive glass is dried up and UV15min with nitrogen.Then the spin coating on ITO Tempo solution.Its process is that rotating speed 3000r/min rotates 60s, forms buffer layer thin film.It is divided to two groups by substrate, one group is not done and locates Reason, another group is placed in the environment full of acetone steam the 20min that anneals, and forms cathode buffer layer.Then two groups of substrates are passed It is sent in the high-quality hand behaviour's case full of N2, with the P3HT that the rotating speed of 800rpm will be stirred:PCBM mixed solutions are spun to the moon On the cushion of pole, spin-coating time is 60s, is dried naturally under room temperature condition afterwards 1 hour, then carries out 120 DEG C of annealings 20 Minute, form light-absorption layer.When the air pressure environment of evaporation is less than 3 × 10-4During Pa, begin to use vacuum evaporation equipment in light-absorption layer Upper evaporation hole mobile material MoO3, form hole transmission layer.The thickness of hole transmission layer is 8nm, and the speed of evaporation is 0.1 Å/s -0.5 Å/s.And then the aluminium electrode of 100nm thickness is deposited with the speed of 5/s-8/s on hole transmission layer.I.e. The available inverse organic solar cell that cathode buffer layer is done with Tempo.Under room temperature environment, the J-V curves of device are surveyed.Its The J-V curves of device are as shown in Figure 7.Unannealed group of device performance is PCE 2.56%, Voc 0.604V, Jsc 8.39mA/ cm2, FF 0.51, the device performance of acetone steam annealing group is PCE 2.13%, Voc 0.604V, Jsc7.14mA/cm2,FF 0.49, can be seen that tetramethyl piperidine Tempo materials are not carried by device performance after acetone solvent annealing from two groups of data Height, is declined slightly on the contrary.
Embodiment 5
To etch and cleaned ITO electro-conductive glass is successively with washing lotion solution, deionized water, acetone, each twice ultrasound of ethanol 15min.By P3HT and PC61BM in mass ratio 1:1 is dissolved in dichlorobenzene solution, the solution of 17mg/ml concentration is made, after mixing Solution at a temperature of 60 DEG C uniform stirring 12 hours, it is stand-by.Cleaned ITO electro-conductive glass is dried up simultaneously with nitrogen UV15min.Using spin coating instrument on ITO spin coating hole transmission layer PEDOT;PSS, rotating speed is 3500r/min, time 60s.It Carry out 120 degree of thermal annealings in atmosphere afterwards 1 hour, form anode buffer layer;Then substrate is sent to full of N2High-quality In hand behaviour's case, with the P3HT that the rotating speed of 800rpm will be stirred:PCBM mixed solutions are spun to PEDOT;On PSS, spin-coating time It is 60s, is dried naturally under room temperature condition afterwards 1 hour, then carry out 120 DEG C and make annealing treatment 20 minutes, forms high-quality extinction Layer.When the air pressure environment of evaporation is less than 3 × 10-4During Pa, begin to use vacuum evaporation equipment that electric transmission is deposited with light-absorption layer Material LiF, forms electron transfer layer, and thickness is 0.8nm, and the speed of evaporation is 0.05/s ~ 0.08/s.And then in LiF On the aluminium electrode of 100nm thickness is deposited with the speed of 5/s-8/s.Can obtain the organic solar batteries of traditional structure.Return Function such as Fig. 6 that one PCE for changing changes with ageing time.From fig. 6, it can be seen that the solar cell of conventional structure was being tested In journey efficiency decline quickly, 20 days afterwards its PCE be reduced to less than the 60% of initial efficiency, show that its stability is very poor.Conversely, Slow for comparing that device its efficiency that the solvent anneal in embodiment 2 is processed is changed over time, its PCE value is still afterwards within 20 days More than the 80% of original date, show that this inverted structure device improves the stability of device well.

Claims (9)

1. a kind of phthalocyanine derivates film as cathode buffer layer inverse organic solar cell, it is characterised in that:It is described fall The structure for putting organic solar batteries is respectively from bottom to top:Transparent substrates, transparent cathode, cathode buffer layer, light-absorption layer, hole Transport layer and metal anode.
2. a kind of phthalocyanine derivates film according to claim 1 is electric as the inverse organic solar of cathode buffer layer Pond, it is characterised in that:In the light-absorption layer, electron donor material is poly- 3- base thiophene P3HT, electron acceptor material for [6, 6]-phenyl C61- methyl butyrate PC61BM, its poly- 3- base thiophene P3HT and [6,6]-phenyl C61- methyl butyrate PC61BM's Mass ratio is 1:1.
3. a kind of phthalocyanine derivates film according to claim 1 is electric as the inverse organic solar of cathode buffer layer Pond, it is characterised in that:The hole transport layer material is molybdenum oxide MoO3
4. a kind of phthalocyanine derivates film according to claim 1 is electric as the inverse organic solar of cathode buffer layer Pond, it is characterised in that:The material of the metal anode is the one kind in Al, Ag and Au.
5. a kind of phthalocyanine derivates film according to claim 1 is electric as the inverse organic solar of cathode buffer layer Pond, it is characterised in that:The material of the transparent cathode is tin indium oxide ITO.
6. a kind of phthalocyanine derivates film according to claim 1 is electric as the inverse organic solar of cathode buffer layer Pond, it is characterised in that:The material of the transparent substrates is clear glass.
7. a kind of phthalocyanine derivates film according to claim any one of 1-6 is organic too as the inversion of cathode buffer layer The preparation method of positive energy battery, it is characterised in that its preparation method is comprised the following steps:
1)Transparent cathode and transparent substrates use ITO electro-conductive glass, will etch ITO electro-conductive glass nitrogen that is good and cleaning up Dry up and carry out the ultraviolet and ozone UV-ozone treatment of 15min;
2)The preparation of cathode buffer layer:Spin coating ZnPc (the OC on ITO electro-conductive glass8H17OPyCH3I)8Solution, its spin coating process is First slow-speed of revolution 700r/min rotates 10s, then rotating speed 3000r/min high rotation 60s, forms buffer layer thin film, is then annealed Treatment;The annealing anneal in the environment full of alcohol vapour 20min to place the substrates in, or with the inertia for circulating Gas stream carries out air-flow annealing 20min to substrate;
3)The preparation of light-absorption layer:Full of N2Glove box in, with the rotating speed of 800rpm by P3HT:PC61BM solution is spun to the moon On the cushion of pole, spin-coating time is 60s, carried out again after then being dried naturally under room temperature condition 1 hour 120 DEG C annealing 20 minutes at Reason, forms light-absorption layer;
4)The preparation of hole transmission layer:Hole mobile material molybdenum oxide is deposited with light-absorption layer using vacuum evaporation equipment;Evaporation Speed be 0.1/s ~ 0.5/s, its evaporation air pressure environment be less than 3 × 10-4Pa;
5)The preparation of metal anode:Using vacuum evaporation equipment on hole transmission layer evaporation metal, formed metal anode, metal The thickness of anode is 80nm ~ 120nm, and evaporation rate is 5/s ~ 8/s, and the air pressure environment of its evaporation is less than 3 × 10-4 Pa。
8. a kind of phthalocyanine derivates film according to claim 7 as cathode buffer layer inverse organic solar cell Preparation method, it is characterised in that:The P3HT:PC61BM solution is prepared by the following method:By poly- 3- base thiophene P3HT and [6,6]-phenyl C61- methyl butyrate PC61BM in mass ratio 1:1 is dissolved in dichlorobenzene solution, makes 17mg/ml dense The solution of degree, mixed solution uniform stirring 12 hours at a temperature of 60 DEG C.
9. a kind of phthalocyanine derivates film according to claim 7 as cathode buffer layer inverse organic solar cell Preparation method, it is characterised in that:ZnPc (the OC8H17OPyCH3I)8Solution is prepared by the following method:By ZnPc (OC8H17OPyCH3I)8It is dissolved in alcohol solvent, makes the ZnPc (OC of 0.8mg/ml concentration8H17OPyCH3I)8Solution.
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CN108807696A (en) * 2018-06-12 2018-11-13 南京邮电大学 A method of improving organic solar batteries modifying interface

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Publication number Priority date Publication date Assignee Title
CN108807696A (en) * 2018-06-12 2018-11-13 南京邮电大学 A method of improving organic solar batteries modifying interface
CN108807696B (en) * 2018-06-12 2022-03-04 南京邮电大学 Method for improving interface modification of organic solar cell

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