CN107359243B - A kind of tertiary blending organic polymer solar cell device - Google Patents
A kind of tertiary blending organic polymer solar cell device Download PDFInfo
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- CN107359243B CN107359243B CN201610301065.9A CN201610301065A CN107359243B CN 107359243 B CN107359243 B CN 107359243B CN 201610301065 A CN201610301065 A CN 201610301065A CN 107359243 B CN107359243 B CN 107359243B
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- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
- H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
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- H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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Abstract
The present invention relates to a kind of tertiary blending organic polymer solar cell devices, it is characterized in that the active layer of solar battery includes three kinds of components, by fullerene acceptor, non- fullerene small molecule receptor is blended with broad-band gap conjugated polymer donor material and is obtained, and the device active layers hypersorption near infrared band ultraviolet to solar spectrum is achieved in.The organic polymer solar cell device prepared with the method, not only preparation process is simple, and the absorption spectrum of solar battery is effectively widened, it can also be according to the pattern of different acceptor ratio regulating cell active layers, regulate and control open-circuit voltage, the photoelectric conversion efficiency of device is made to be greatly improved.The present invention will be widely used in the organic polymer solar cell devices field prepared with solwution method.
Description
Technical field
The invention belongs to organic semiconductor device fields, and what is involved is one of organic polymer solar cell ternarys
Active layer structure is blended.
Background technique
As energy shortages and problem of environmental pollution are increasingly sharpened, solar energy is obtained as a kind of clean renewable energy
Extensive attention.Organic polymer solar cell has obtained extensive and in-depth research and has achieved hair at full speed recent years
Exhibition, photoelectric conversion efficiency achieves very big raising, but there are also a distances apart from commercialization.It is undeniable to be, battery
The further promotion of efficiency is the new bottleneck that the current organic polymer sun encounters, only by innovative thinking, using new plan
It slightly can just reach a solution of a problem, open the space that efficiency is promoted further up, just may make organic polymer solar cell
Energy conversion efficiency reach the stage of commercial applications.
Under normal conditions, the active layer of polymer solar battery is two-spot blend film, including a kind of polymeric donor
Material and a kind of electron acceptor material.The shortcomings that such polymer solar battery be it is relatively narrow to the absorption region of sunlight,
It cannot generally cover ultraviolet to the full spectral coverage of near-infrared.Based on the present Research in current polymer solar battery field, ternary is total
It is mixed with machine solar cell device research field and obtains extensive concern in recent years.The concept of ternary blend systems is opened up with laminated device
The purpose of wide solar battery absorption spectrum is identical, but the manufacturing process of laminated cell is complex, is unfavorable for using solution
The method of spin coating carries out the continuous production processing of large area.In order to widen the spectral absorption of organic polymer solar cell, together
When adjust polymer solar battery active layer in microcosmic nanostructure, it has been found that ternary blend systems have unique effect
Fruit, can improve several important parameters of polymer solar battery to a certain extent, including open-circuit voltage, short circuit current,
Fill factor etc..However, reported tertiary blending polymer solar battery generally uses two kinds of electron donor materials and one
Kind electron acceptor mixing is used as active layer (Adv.Mater.2015,27,1071-1076；Nat.Commun.2015,6,7327；
Nat.Photon.2014,8,716；Adv.Mater.2013,25,4245–4266；Nat.Photon.2015,9,491), used
Electron acceptor material is usually fullerene derivate, due to limit of the fullerene compound in terms of open-circuit voltage and absorption spectrum
System, this can make the photoelectric conversion efficiency of device be difficult to break through there are bottleneck.
It is different from previously reported tertiary blending polymer solar battery, in recent years about using a kind of electron donor
Material mixed with two kinds of electron acceptors as polymer solar battery active layer report (Energy Environ.Sci.,
2014,7,2005-2011), second introduced of receptor can play bridge between polymeric donor and the first receptor
Effect, increase electron donor-acceptor (EDA) between charge transferring channel, and then promoted device efficiency.However, it is used both
Electron acceptor material is still all fullerene derivate, still remains the limitation in terms of open-circuit voltage and absorption spectrum.
Therefore, it is existing for breaking through as the active layer of polymer solar battery that a kind of novel ternary blend systems are developed
Spectral absorption that is restricted, widening battery-active layer improves its photoelectric conversion efficiency and is of great significance.
Summary of the invention
A kind of active layer the object of the present invention is to provide ternary mixture as organic solar batteries device improves
The incident photon-to-electron conversion efficiency of device.
Technical solution of the present invention: solar battery active layer of the present invention uses a kind of wide band gap polymer donor
Material is blended with two kinds of electron acceptor materials, used in two kinds of electron acceptor materials be respectively fullerene electron acceptor and
Non- fullerene small molecule electron-acceptor.The introducing of non-fullerene small molecule electron-acceptor can make solar battery in open-circuit voltage
It is limited with absorption spectrum etc. breakthrough, and widens the spectral absorption range of battery-active layer, can effectively promote unijunction polymer
The photoelectric conversion efficiency of solar battery.Active layer pattern is optimized by adjusting the different proportions of both receptors,
It can reach optimal photoelectric conversion efficiency.
A kind of tertiary blending organic polymer solar cell device of the present invention, device architecture successively include:
Prescribed electrode, electron-transport or hole blocking layer, tertiary blending active layer, electronic blocking or hole transmission layer, metal electrode.
The tertiary blending active layer includes broad-band gap conjugated polymer electron donor, fullerene electron acceptor and non-
These three components of fullerene small molecule electron-acceptor.Non- fullerene small molecule electron-acceptor institute in the tertiary blending active layer
The mass percent accounted for be X, 1% < X < 80%, the tertiary blending active layer with a thickness of 50~1000nm.
The band gap (Eg) of broad-band gap conjugated polymer electron donor in the tertiary blending active layer is greater than 1.6eV；Institute
Stating fullerene electron acceptor is fullerene and its derivative；The non-fullerene small molecule electron-acceptor is not comprising fowler
The conjugation small molecule compound of alkenyl group, the absorbing band with near-infrared, molecular weight ranges are 200~5000, band
Gap range is 1.2~1.8eV, and maximum absorption peak position is greater than 700nm.
The transparent electrode material is the conductive material transparent or semitransparent in visible region, and light transmittance is greater than 50%；Institute
It states in zinc oxide (AZO), the graphite that the transparent or semitransparent conductive material of visible region is tin indium oxide (ITO), aluminium adulterates
One of alkene, carbon nanotube, metal nanowire thin-films, metallic film.
The electron-transport or hole blocking layer are the organic compound with electron transport ability or hole blocking ability
Or metal oxide, the electron-transport or hole blocking layer thickness range are as follows: 1~200nm.
The electronic blocking or hole transmission layer are the organic compound with cavity transmission ability or electron-blocking capability
Or metal oxide, the electronic blocking or thickness of hole transport layer range are as follows: 1~200nm.
The metal electrode material is gold, silver, platinum, copper, aluminium.
The present invention have the advantages that following characteristics and:
1. the present invention gives receptor binary using a kind of organic polymer solar cell device of tertiary blending, with conventional
Co-mixing system is compared, and is had to the spectral absorption range of active layer and is greatly widened, and enables the device to capture more long-wave band too
Sunlight, so that the photoelectric conversion efficiency of solar battery be greatly improved.
2. the ratio adjusted between two kinds of electron acceptors in the present invention can effectively regulate and control the open-circuit voltage of device, and fill out
The factor is filled, so as to improve solar cell properties.This provides newly the popularization and application of organic polymer solar cell from now on
Thinking.
3. the amboceptor structure that the present invention uses has certain regulating and controlling effect to the pattern of active layer, compensate for polymer to
The larger disadvantage of phase separation scale is blended in body and small molecule receptor, facilitates the effective biography of charge efficiently separated with carrier
It is defeated, so that the short circuit current of device be made to have biggish promotion, help to obtain high incident photon-to-electron conversion efficiency (> 10%).
4. solar cell device according to the present invention, manufacture craft is simple, and device active layers are solwution method preparation.This
Kind method can be improved the utilization rate of material, reduce cost, improve production capacity.
Specific embodiment:
Embodiment 1: using three kinds of materials shown in Fig. 1 as the work of tertiary blending organic polymer solar cell device
Property layer material.Wherein, the band gap (Eg) of wide band gap polymer donor material PPBDTBT (referred to as P1) is 1.8eV；Non- fullerene
The molecular weight of small molecule receptor material ITIC is 1430, and band gap (Eg) is 1.7eV.
ITO/ZnO(30nm)/P1:ITIC:PC71BM(120nm)/MoO3(8.5nm)/Ag (100nm) device architecture such as Fig. 2
It is shown.The content (mass percent) of non-fullerene small molecule receptor material ITIC is 10%~60% in this device active layers.
The preparation process of device is as follows:
1.ITO (transparent electrode) substrate of glass is cleaned first with detergent, then successively uses tap water, deionized water, ethyl alcohol
It rinses, to remove surface grease and dust.Later with deionized water, acetone, each ultrasound 15min of isopropanol, and it is dry to be put into vacuum
80 DEG C of heating in vacuum 40min are in dry case to dry substrate.Next, by the ITO substrate dried UV ozone cleaning machine
(UVO) 30min is handled.
2. with the ZnO (electron transfer layer), Zhi Hou of the revolving speed of 3500rpm one layer of about 30nm thickness of spin coating in ITO substrate
Anneal at a temperature of 200 DEG C 30min in air.
3. that prepare o-dichlorohenzene dissolution includes P1:ITIC:PC71The mixed solution of BM, total concentration 35mg/mL, ITIC
The mass percent for accounting for solid amount is 10%~60%.ZnO layer is spin-coated on the parameter of 2500rpm, 60s with this mixed solution
On be used as active layer, thickness is about 120nm.
4. being 3 × 10 in vacuum degree-7Under conditions of Torr successively in a manner of hot evaporation by MoO3(8.5nm) and Ag
(100nm), is deposited on active layer, as electronic barrier layer and metal electrode.
The test of device performance: in glove box with 2400 digital multimeter of Keithley under AM1.5G illumination condition
The current -voltage curve of measurement device, and open-circuit voltage, the short-circuit current density of device is calculated with this, fill factor and
The parameters such as photoelectric conversion efficiency, the effective area of device are 0.04cm2.Resulting tertiary blending organic polymer solar cell
The optimal performance of device is as follows: open-circuit voltage 0.89V, short-circuit current density 16.81mA/cm-2, fill factor 0.69,
Photoelectric conversion efficiency is 10.41%.
Embodiment 2: preparing reference device as described in Example 1, except that the active layer of device is binary blending
System, respectively P1:PCBM and P1:ITIC.Resulting organic polymer solar cell device optimal performance is as follows:
P1:PCBM system: open-circuit voltage 0.77V, short-circuit current density 12.64mA/cm-2, fill factor 0.75,
Photoelectric conversion efficiency is 7.29%.
P1:ITIC system: open-circuit voltage 0.93V, short-circuit current density 12.56mA/cm-2, fill factor 0.64,
Photoelectric conversion efficiency is 7.47%.The performance of device is significantly worse than the device performance in embodiment 1 in embodiment 2, such as Fig. 3 institute
Show.
Embodiment 3: being verifying ternary blend systems to spectrum complementation and the promotion of battery efficiency, we are to embodiment 1
Device and 2 device of embodiment have carried out the test of external quantum efficiency (IPCE).
Test is 1mm in spot size in atmospheric environment2It is carried out under tungsten light source simulator.We can be with from Fig. 4
It was found that 1 device of embodiment compared with 2 device of embodiment have in spectral absorption it is very big widen, external quantum efficiency reaches 75%.
The preparation method of tertiary blending organic solar batteries device provided by the invention is had been described in detail above,
And confirm the photoelectric conversion efficiency that device can be effectively improved using which.Specific case cited herein is to of the invention
Principle and embodiment are expounded, but these examples are not intended to restrict the invention.It is any not depart from the principle of the invention
Under the premise of, simple modification is carried out to the present invention and is also belonged in claims of the invention.
Detailed description of the invention:
Fig. 1 is three kinds of components (broad-band gap conjugated polymer donor material P1, fullerenes selected by active layer in embodiment 1
Electron-like acceptor material PC71BM and non-fullerene small molecule electron-acceptor material ITIC) molecular structure.
Fig. 2 is organic polymer solar cell device architecture schematic diagram prepared by embodiment 1.
Fig. 3 is the photovoltaic property curve graph of organic polymer solar cell device in embodiment 1,2
Fig. 4 is the external quantum efficiency curve graph of organic polymer solar cell device in embodiment 1,2,3.
Claims (6)
1. a kind of tertiary blending organic polymer solar cell device, it is characterised in that: the tertiary blending organic polymer
The device architecture of solar battery successively includes: transparent electrode, electron-transport or hole blocking layer, tertiary blending active layer, electricity
Son stops or hole transmission layer, metal electrode, wherein the tertiary blending active layer includes that broad-band gap conjugated polymer electronics is given
Body, fullerene electron acceptor and non-these three components of fullerene small molecule electron-acceptor, the thickness of the tertiary blending active layer
Degree is 50~1000nm.
2. a kind of tertiary blending organic polymer solar cell device as described in right 1, it is characterized in that the tertiary blending
The band gap (Eg) of broad-band gap conjugated polymer electron donor in active layer is greater than 1.6eV；The fullerene electron acceptor is
Fullerene and its derivative；The non-fullerene small molecule electron-acceptor is the conjugation small molecule not comprising fowler alkenyl group
Object is closed, the absorbing band with near-infrared, molecular weight ranges are 200~5000, and bandgap range is 1.2~1.8eV, most
High-selenium corn peak position is greater than 700nm.
3. a kind of tertiary blending organic polymer solar cell device as described in right 1, it is characterized in that the transparent electrode
Material is the conductive material transparent or semitransparent in visible region, and light transmittance is greater than 50%；It is described transparent or half in visible region
Zinc oxide (AZO), the graphene, carbon nanotube, metal nano that transparent conductive material is tin indium oxide (ITO), aluminium adulterates
One of line film, metallic film.
4. a kind of tertiary blending organic polymer solar cell device as described in right 1, it is characterized in that the electron-transport
Or hole blocking layer is organic compound or metal oxide with electron transport ability or hole blocking ability, which passes
Defeated or hole blocking layer thickness range are as follows: 1~200nm.
5. a kind of tertiary blending organic polymer solar cell device as described in right 1, it is characterized in that the electronic blocking
Or hole transmission layer is organic compound or metal oxide with cavity transmission ability or electron-blocking capability, electronics resistance
Gear or thickness of hole transport layer range are as follows: 1~200nm.
6. a kind of tertiary blending organic polymer solar cell device as described in right 1, it is characterized in that the metal electrode
Material is gold, silver, platinum, copper, aluminium.
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| CN108365098B (en) * | 2018-01-10 | 2019-11-15 | 浙江大学 | A kind of efficient ternary organic photovoltaic cell |
| CN108550699A (en) * | 2018-04-12 | 2018-09-18 | 山东大学 | A kind of ternary organic solar energy cell structure and preparation method thereof based on the non-fullerene acceptor of small molecule |
| CN108550702A (en) * | 2018-04-28 | 2018-09-18 | 华南协同创新研究院 | Translucent organic solar batteries and its preparation method and the application in photovoltaic agricultural greenhouse |
| CN108832000B (en) * | 2018-06-19 | 2021-11-05 | 南京邮电大学 | Ternary polymer solar cell |
| CN110858626B (en) * | 2018-08-24 | 2021-12-14 | 中国科学院化学研究所 | Blend, blend film containing blend, photovoltaic active layer and device and preparation method of blend |
| GB201819628D0 (en) * | 2018-11-30 | 2019-01-16 | Sumitomo Chemical Co | Photodetector composition |
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