CN105140404A - Bulk heterojunction organic thin-film solar cell and preparation method thereof - Google Patents

Bulk heterojunction organic thin-film solar cell and preparation method thereof Download PDF

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Publication number
CN105140404A
CN105140404A CN201510432094.4A CN201510432094A CN105140404A CN 105140404 A CN105140404 A CN 105140404A CN 201510432094 A CN201510432094 A CN 201510432094A CN 105140404 A CN105140404 A CN 105140404A
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solar cell
bulk heterojunction
organic thin
film solar
thin film
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张宏梅
戴运杰
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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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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

The invention discloses a bulk heterojunction organic thin-film solar cell and a preparation method thereof. The cell has an inverted structure and is composed of a transparent substrate, a transparent cathode, a cathode modification layer, an active layer, a hole transmission layer and a metal anode which are arranged from the bottom to the top in turn. The modification effect of hindered amine light stabilizer material to the transparent electrode is utilized so that the work function of the transparent cathode is reduced, energy level of the transparent cathode is coordinated, cathode interface barrier is reduced and electron transmission and collection capability of the cathode is enhanced. Besides, the suppression effect of the hindered amine light stabilizer to photochemical reaction is utilized so that stability of the cathode interface is also enhanced by the modification layer and aging resistance of the cell can be enhanced. The modification layer is prepared by a spin coating and self-assembling method so that the preparation technology is simple. Besides, the light stabilizer is material of mass industrial production so that reduction of cost of the solar cell is facilitated.

Description

A kind of bulk heterojunction organic thin film solar cell and preparation method thereof
Technical field
The present invention relates to a kind of organic thin film solar cell, be specifically related to a kind of hindered amine as light stabilizer that adopts as the inverted structure bulk heterojunction organic thin film solar cell of cathodic modification layer, belong to technical field of solar.
Background technology
Energy problem is one of sixty-four dollar question of facing of the world today, and the increasingly serious environmental problem caused along with the continuous consumption of fossil energy and the Long-Time Service of fossil energy, finds large, the free of contamination new forms of energy of a kind of reserves extremely urgent.Numerous new forms of energy, comprise nuclear energy, solar energy, biological energy source, water power energy, wind energy, geothermal energy and tidal energy etc.Wherein, solar energy because of its inexhaustible huge reserves, the environmental protection characteristic of cleanliness without any pollution, simple production technology and lower production cost, convenient, flexible application mode, the extremely favor of people are one of energy technologys of New Times most prospect.
Solar battery technology is a kind of technology solar energy being directly converted to electric energy, utilize one of the most effective mode of solar energy, the inorganic photoelectric device that it is active material that the research of conventional solar cell mainly concentrates on silicon, GaAs, cadmium telluride and lamination GaInP/GaAs/Ge etc.But such devices cost of material is higher, production technology is comparatively complicated, is difficult to prepare flexible device etc., significantly limit development and the application of this type of solar battery technology.
Bulk heterojunction organic thin film solar cell is a kind of novel solar battery technology that development in recent years is swift and violent.Compared with other solar battery technologies, it has lightweight, and cost is low, and preparation technology is simple, can be prepared into the advantages such as flexible device, therefore become one of the most promising technology of current area of solar cell.
Bulk heterojunction organic thin film solar cell generally includes negative electrode, anode and is clipped in two interelectrode electroluminescent unit.The present invention uses the transparent cathode film modified with hindered amine as light stabilizer, as the negative electrode of organic thin film solar cell, prepares a kind of bulk heterojunction organic thin film solar cell of inverted structure.
Photoelectric conversion efficiency is one of main parameter determining solar cell quality, and it is determined by open circuit voltage, short circuit current, these three parameters of fill factor, curve factor.It is improve the key of solar cell photoelectric transformation efficiency that comprehensive coordination improves these three parameters, and for this reason, researchers have carried out effort in all its bearings.
The theoretical boundary of bulk heterojunction organic thin film solar cell open circuit voltage, is determined by the difference of the HOMO of donor material in active layer and the LOMO of acceptor material.For given active layer material, the energy level of active layer both sides part produces main impact to it.Therefore, between each part of organic optical thin film solar cell, usually facing the unmatched problem of energy level, form higher potential barrier in interface, being unfavorable for that interface forms ohmic contact, because this reducing open circuit voltage.So organic optical thin film solar cell needs the problem solving each part level-density parameter.
Researchers find, decorative layer is added between active layer and electrode, effectively can suppress the compound in electronics and hole in carrier transport process, the efficiency of transmission of raising electric charge and electrode collect the ability of electric charge, form excellent diode structure, thus improve short circuit current and the fill factor, curve factor of battery.Usually, cathodic modification material major requirement 1) and can have between edge layer and form ohmic contact; 2) effectively negative electrical charge can be transmitted; 3) effectively positive charge can be blocked while effectively collecting negative electrical charge; 4) form excellent membrane structure in interface, the series resistance of device can not be improved, the parallel resistance of device can not be reduced.
Cathodic modification layer conventional at present, mineral-type, as LiF, Ca, Mg etc., is prepared by the mode of vacuum thermal evaporation usually, and need higher temperature and vacuum degree, process costs is higher, and is difficult to extensive preparation; Organic is as some derivatives of fullerene, and production cost is higher.Lower and the simple cathodic modification material of preparation technology of a kind of production cost relatively of market demand.
In addition, the interface between each part of organic optical thin film solar cell, is easy to the erosion being subject to water oxygen, also easily photochemical reaction occurs, destroy original interfacial structure, forms surface state, thus weakens the stability of organic thin film solar cell.
Summary of the invention
Technical problem: the present invention is exactly for the problems referred to above, devises a kind of inverted structure bulk heterojunction organic thin film solar cell based on hindered amine as light stabilizer cathodic modification layer and preparation method thereof.
Technical scheme: light stabilizer is a kind of high molecular products (such as plastics, rubber, coating, synthetic fibers etc.) additive conventional at present, for suppressing and slowing down photochemically reactive generation, thus improves the ageing resistance of high molecular products.It is a kind of chemicals of current large-scale industrial production, and price is low, and purchase, transport, storage etc. are all more convenient.Light stabilizer material is introduced solar cell industry by the present invention first, utilize the interaction of amine groups and transparent cathode on hindered amine light stabilizer material, as the decorative material of transparent cathode, to greatly improve in inverted structure organic thin film solar cell transparent cathode to the transmission of electronics and capacity gauge.
In addition, in organic thin film solar cell, interface is link the most fragile, very easily be subject to photochemically reactive erosion, produce interface surface state, destroy original interfacial structure, thus reduce transmission and the capacity gauge of electric charge, cause the compound of charge carrier, adverse influence is produced to the short circuit current of battery and fill factor, curve factor.The present invention utilizes light stabilizer to photochemically reactive inhibitory action, as modifying interface material, improves interface and resists photochemically reactive ability, thus improve the stability at interface.
Light stabilizers material, the organic solvent that major part is conventional can be dissolved in, as the embellishing cathode interface material of organic thin film solar cell, the method of spin coating or self assembly can be used to prepare, and without the need to annealing, need higher vacuum and temperature compared to LiF, Ca, Mg etc., by the conventional mineral-type cathodic modification material of the method masking of vacuum thermal evaporation, preparation technology simplifies greatly; Light stabilizer material is the chemicals of suitability for industrialized production, can adopt the mineral-type decorative material of spin coating and self assembly method compared to the various derivatives etc. of other such as fullerenes equally, and the purchase cost of itself is lower.Therefore, light stabilizers material, as the cathodic modification material of organic thin film solar cell, has great cost advantage, and for future, road has been paved in the industrialization of organic thin film solar cell.
The negative electrode of a kind of bulk heterojunction organic thin film solar cell of the present invention is modified by hindered amine as light stabilizer material, and sequence from low to uper part is set to: transparent substrates, transparent cathode, cathodic modification layer, active layer, hole transmission layer, metal anode;
Wherein,
Described transparent substrates is glass or flexible PET substrate;
Described transparent cathode is the one in ITO, IO, IZO, AZO or FTO;
Described cathodic modification layer is hindered amine as light stabilizer material,
Described active layer is the bulk heterojunction active layer be prepared from by the mixture of the derivative of thiophene compound and fullerene;
Described hole transmission layer is MoO 3, V 2o 5, WO 3in one;
Described metal anode electrode is the one in Al, Ag, Au;
Wherein:
Described thiophene compound is poly-3 base thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC61BM or PC71BM.
Described hindered amine as light stabilizer material is hindered amine as light stabilizer TH-944, i.e. [C 35h 68n 8] n.
The preparation method of a kind of bulk heterojunction organic thin film solar cell of the present invention comprises the following steps:
1). transparent cathode and transparent substrates use ITO electro-conductive glass finished product, and on the ITO electro-conductive glass cleaned up, spin coating light stabilizer solution, after naturally drying, forms cathodic modification layer at substrate surface; Or the ITO electro-conductive glass cleaned up is put into hindered amine as light stabilizer solution soak, produce self assembling process, afterwards taking-up solvent washing, form cathodic modification layer at substrate surface.
2). spin coating bulk heterojunction active layer solution on hindered amine as light stabilizer cathodic modification layer, utilizes vacuum thermal evaporation evaporation one deck MoO on bulk heterojunction active layer surface after annealing 3film is as hole transmission layer;
3). on hole transmission layer, utilize vacuum thermal evaporation to collect hole at its surperficial evaporation metal anode electrode, namely complete the preparation of described solar cell.
5. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 4, is characterized in that, in step 1) in, spin coating light stabiliser solution concentration is 0.3% ~ 0.7%w/w, solvent is preferably acetone, spin coating rotating speed 3500rpm, time 60s; Self assembly light stabiliser solution concentration is 1.5% ~ 2.5%w/w, and solvent is preferably acetone, self assembly time 1.5h ~ 3h.
In step 2) in, spin coating bulk heterojunction active layer solution materials is the mixture of the derivative of thiophene compound and fullerene, and wherein thiophene compound is poly-3 base thiophene P3HT or polyphenyl 1,4-Dithiapentalene PTB7; The derivative of fullerene is PC61BM or PC71BM.
Bulk heterojunction active layer solution is prepared by following method:
In mass ratio, P3HT is dissolved in dichloro-benzenes after mixing with the ratio of 1:1 with PC61BM with the concentration of 17mg/ml, and mixed solution 60 DEG C adds thermal agitation 12 hours; Or PTB7 is dissolved in dichloro-benzenes after mixing with the ratio of 1:1.5 with PC71BM with the concentration of 12mg/ml, add 1, the 8-diiodo-octane DIO that volume ratio is 3%, mixed solution 70 DEG C stirs 5 hours.
MoO 3film thickness is 8nm, and evaporation rate is 0.05nm/s.
Metal anode thickness of electrode is 120nm ~ 150nm, and evaporation rate is 0.8nm/s.
The hindered amine as light stabilizer material block amine light stabilizer TH-944 introduced in the preferred bill of the present invention, is easy to become solution in acetone, the organic solvents such as chlorobenzene, prepares decorative layer by the method for spin coating or self assembly, and without the need to annealing, technique is simple, with low cost; Utilize the effect of amine groups and ITO, coordinated the energy level of ITO negative electrode, improve electron collection and the transmittability of negative electrode; Meanwhile, hindered amine suppresses photochemical reaction by catching the number of ways such as the energy of free radical, hydroperoxide decomposition and transmission excited state molecule, improves the stability of cathode interface, improves the ageing resistance of battery.
Beneficial effect:
1. the hindered amine light stabilizer material of the present invention's use, be the material of large-scale industrial production, cost is lower;
2. the present invention utilizes hindered amine as light stabilizer material to prepare organic thin film solar cell cathodic modification layer, and by the method for spin coating, self assembly, preparation technology is simple, without the need to the process such as evaporation, annealing, is conducive to reducing production cost.
3. the hindered amine as light stabilizer cathodic modification layer of the present invention's utilization, has coordinated the energy level of ITO negative electrode, has been conducive to transmission and the collection of electronics, improves the performance of organic thin film solar cell.
4. the present invention utilizes hindered amine as light stabilizer to photochemically reactive inhibitory action, improves the stability of organic thin film solar cell cathode interface, improves the ageing resistance of battery.
5. a use Al is as anode, with low cost.
Accompanying drawing explanation
Fig. 1 is the structural representation of the bulk heterojunction organic thin film solar cell of embodiment one gained,
Fig. 2 is the J-V curve chart of the bulk heterojunction organic thin film solar cell of embodiment one gained,
Fig. 3 is the J-V curve chart of the bulk heterojunction organic thin film solar cell of embodiment two gained.
Embodiment
Embodiment one
Take acetone as solvent, compound concentration 0.5% (w/w) hindered amine as light stabilizer TH-944 solution for standby.P3HT is with the concentration of 17mg/ml, and PC61BM is to be dissolved in dichloro-benzenes after the mixing of the ratio of 1:1 (W:W), and mixed solution 60 DEG C adds thermal agitation 12 hours, stand-by.ITO transparent substrates is used successively each twice ultrasonic 15min of washing lotion solution, deionized water, acetone, ethanol, dry up with nitrogen.Adopt spin-coating method that the resistance amine light stabilizer TH-944 solution prepared is spin-coated on ITO substrate, rotating speed is 3500rpm, and the time is 60s.Naturally dry 2h in atmosphere, form cathodic modification layer.Spin coating bulk heterojunction active layer P3HT:PC61BM on cathodic modification layer, rotating speed is 800rpm, and the time is 60s.Naturally dry 1h in nitrogen environment after, 120 DEG C of annealing 20min.The hot evaporation thickness of high vacuum is utilized to be about the MoO of 8nm successively 3with the Al electrode of 130nm, namely obtain described organic thin film solar cell, it has inversion structures.
Under room temperature environment, record the J-V curve of device.
Embodiment two
Take acetone as solvent, compound concentration 2% (w/w) hindered amine as light stabilizer TH-944 solution for standby.P3HT is with the concentration of 17mg/ml, and PC61BM is to be dissolved in dichloro-benzenes after the mixing of the ratio of 1:1 (W:W), and mixed solution 60 DEG C adds thermal agitation 12 hours, stand-by.ITO transparent substrates is used successively each twice ultrasonic 15min of washing lotion solution, deionized water, acetone, ethanol, dry up with nitrogen.ITO transparent substrates is placed in the hindered amine as light stabilizer TH-944 solution prepared and soaks 2h, form self assembling process.Soaked ITO transparent substrates is taken out, naturally dries with after acetone rinsing, form cathodic modification layer.Spin coating bulk heterojunction active layer P3HT:PC61BM on cathodic modification layer, rotating speed is 800rpm, and the time is 60s.Naturally dry 1h in nitrogen environment after, 120 DEG C of annealing 20min.The hot evaporation thickness of high vacuum is utilized to be about the MoO of 8nm successively 3with the Al electrode of 130nm, namely obtain described organic thin film solar cell, it has inversion structures.
Under room temperature environment, record the J-V curve of device.

Claims (9)

1. a bulk heterojunction organic thin film solar cell, it is characterized in that the negative electrode of this bulk heterojunction organic thin film solar cell is modified by hindered amine as light stabilizer material, sequence from low to uper part is set to: transparent substrates, transparent cathode, cathodic modification layer, active layer, hole transmission layer, metal anode;
Wherein,
Described transparent substrates is glass or flexible PET substrate;
Described transparent cathode is the one in ITO, IO, IZO, AZO or FTO;
Described cathodic modification layer is hindered amine as light stabilizer material,
Described active layer is the bulk heterojunction active layer be prepared from by the mixture of the derivative of thiophene compound and fullerene;
Described hole transmission layer is MoO 3, V 2o 5, WO 3in one;
Described metal anode electrode is the one in Al, Ag, Au.
2. a kind of bulk heterojunction organic thin film solar cell according to claim 1, is characterized in that described thiophene compound is poly-3 base thiophene or polyphenyl 1,4-Dithiapentalenes; The derivative of fullerene is PC61BM or PC71BM.
3. a kind of bulk heterojunction organic thin film solar cell according to claim 1, is characterized in that described hindered amine as light stabilizer material is hindered amine as light stabilizer TH-944, i.e. [C 35h 68n 8] n.
4. a preparation method for bulk heterojunction organic thin film solar cell as claimed in claim 1, is characterized in that the preparation method of this solar cell comprises the following steps:
1). transparent cathode and transparent substrates use ITO electro-conductive glass finished product, and on the ITO electro-conductive glass cleaned up, spin coating light stabilizer solution, after naturally drying, forms cathodic modification layer at substrate surface; Or the ITO electro-conductive glass cleaned up is put into hindered amine as light stabilizer solution soak, produce self assembling process, afterwards taking-up solvent washing, form cathodic modification layer at substrate surface.
2). spin coating bulk heterojunction active layer solution on hindered amine as light stabilizer cathodic modification layer, utilizes vacuum thermal evaporation evaporation one deck MoO on bulk heterojunction active layer surface after annealing 3film is as hole transmission layer;
3). on hole transmission layer, utilize vacuum thermal evaporation to collect hole at its surperficial evaporation metal anode electrode, namely complete the preparation of described solar cell.
5. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 4, is characterized in that, in step 1), spin coating light stabiliser solution concentration is 0.3% ~ 0.7%w/w, solvent is preferably acetone, spin coating rotating speed 3500rpm, time 60s; Self assembly light stabiliser solution concentration is 1.5% ~ 2.5%w/w, and solvent is preferably acetone, self assembly time 1.5h ~ 3h.
6. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 4, it is characterized in that, in step 2) in, spin coating bulk heterojunction active layer solution materials is the mixture of the derivative of thiophene compound and fullerene, and wherein thiophene compound is poly-3 base thiophene P3HT or polyphenyl 1,4-Dithiapentalene PTB7; The derivative of fullerene is PC61BM or PC71BM.
7. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 6, is characterized in that, bulk heterojunction active layer solution is prepared by following method:
In mass ratio, P3HT is dissolved in dichloro-benzenes after mixing with the ratio of 1:1 with PC61BM with the concentration of 17mg/ml, and mixed solution 60 DEG C adds thermal agitation 12 hours; Or PTB7 is dissolved in dichloro-benzenes after mixing with the ratio of 1:1.5 with PC71BM with the concentration of 12mg/ml, add 1, the 8-diiodo-octane DIO that volume ratio is 3%, mixed solution 70 DEG C stirs 5 hours.
8. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 4, is characterized in that, MoO 3film thickness is 8nm, and evaporation rate is 0.05nm/s.
9. the preparation method of a kind of bulk heterojunction organic thin film solar cell according to claim 4, is characterized in that, metal anode thickness of electrode is 120nm ~ 150nm, and evaporation rate is 0.8nm/s.
CN201510432094.4A 2015-07-21 2015-07-21 Bulk heterojunction organic thin-film solar cell and preparation method thereof Pending CN105140404A (en)

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CN105576130A (en) * 2016-03-11 2016-05-11 张虹 Organic photovoltaic cell
CN106206954A (en) * 2016-07-28 2016-12-07 太原理工大学 A kind of inversion bulk heterojunction organic solar batteries
CN109449297A (en) * 2018-11-15 2019-03-08 山东大学 A kind of organic solar energy cell structure and preparation method thereof based on polypropylene as third member
CN109873081A (en) * 2019-03-21 2019-06-11 南京邮电大学 A kind of organic photovoltaic battery and preparation method thereof based on organic/inorganic diffusion boundary layer
CN110098334A (en) * 2019-05-13 2019-08-06 电子科技大学 A kind of cathodic modification layer material and preparation method thereof and solar battery and preparation method thereof
CN111211229A (en) * 2020-01-15 2020-05-29 深圳市华星光电半导体显示技术有限公司 Photoelectric device and manufacturing method thereof
CN111816726A (en) * 2020-06-15 2020-10-23 隆基绿能科技股份有限公司 Back contact solar cell, production method thereof and back contact cell assembly

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Publication number Priority date Publication date Assignee Title
CN105576130A (en) * 2016-03-11 2016-05-11 张虹 Organic photovoltaic cell
CN106206954A (en) * 2016-07-28 2016-12-07 太原理工大学 A kind of inversion bulk heterojunction organic solar batteries
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CN109449297A (en) * 2018-11-15 2019-03-08 山东大学 A kind of organic solar energy cell structure and preparation method thereof based on polypropylene as third member
CN109449297B (en) * 2018-11-15 2019-08-09 山东大学 A kind of organic solar energy cell structure and preparation method thereof based on polypropylene as third member
CN109873081A (en) * 2019-03-21 2019-06-11 南京邮电大学 A kind of organic photovoltaic battery and preparation method thereof based on organic/inorganic diffusion boundary layer
CN109873081B (en) * 2019-03-21 2022-08-26 南京邮电大学 Organic photovoltaic cell based on organic/inorganic gradient diffusion interface layer and preparation method thereof
CN110098334A (en) * 2019-05-13 2019-08-06 电子科技大学 A kind of cathodic modification layer material and preparation method thereof and solar battery and preparation method thereof
CN111211229A (en) * 2020-01-15 2020-05-29 深圳市华星光电半导体显示技术有限公司 Photoelectric device and manufacturing method thereof
CN111816726A (en) * 2020-06-15 2020-10-23 隆基绿能科技股份有限公司 Back contact solar cell, production method thereof and back contact cell assembly
CN111816726B (en) * 2020-06-15 2023-10-03 隆基绿能科技股份有限公司 Back contact solar cell, production method thereof and back contact cell assembly

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Application publication date: 20151209