CN104078565B - Organic photoelectric switching device - Google Patents
Organic photoelectric switching device Download PDFInfo
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- CN104078565B CN104078565B CN201310095826.6A CN201310095826A CN104078565B CN 104078565 B CN104078565 B CN 104078565B CN 201310095826 A CN201310095826 A CN 201310095826A CN 104078565 B CN104078565 B CN 104078565B
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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
- H10K30/20—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
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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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- 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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Abstract
This application discloses a kind of electrooptical device, including：Hearth electrode；Top electrode；Photoactive layer between the hearth electrode and top electrode；The spectral sensitization layer of absorption spectrum and photoactive layer complementation between the hearth electrode and photoactive layer, and/or the top electrode and photoactive layer.Spectral sensitization layer participates in the transmission process of charge in device.Spectral sensitization layer can improve responding ability of the device to spectrum with having spectral absorption complementation performance between photoactive layer.
Description
Technical field
The application belongs to electrooptical device field, more particularly to a kind of photoelectric converter with spectral sensitization layer
Part.
Background technology
Photoelectric conversion technique based on semiconductor technology is constantly progressive, and is based especially on the organic thin of organic semiconducting materials
Film photovoltaic cell.At present, novel organic photoelectric semi-conducting material continuously emerges, and light absorption and photoelectric conversion efficiency constantly increase
Add.As photoactive layer, organic conjugate semi-conducting material mainly undertakes light absorption, generates exciton, and exciton dissociation generation freely moves
The effect of dynamic charge.Wherein light absorption is that the basis of subsequent serial process seems, therefore extremely important.People are mainly led at present
The organic conjugated molecule of synthesis narrow band gap is crossed to improve spectral absorption efficiency.
The absorption spectrum of organic conjugated molecule is mainly to be generated by transition of the valence electron in molecule on conjugated pi track
, therefore, the absorption spectrum of organic semiconducting materials is in band-like, i.e., material has apparent absorption wave crest and absorption trough.Base
In this organic film photovoltaic device, the conversion quantum efficiency at organic semiconducting materials absorption trough is relatively low, affects device
The opto-electronic conversion performance of part.
Solve the problems, such as that this common methods include：1. the blending using multiple material prepares compound photoactive layer technology：
There will be the material of different spectral response abilities, compound photoactive layer is formed come the spectrum of extended device by being blended to prepare
Responding ability；2. utilize multijunction cell connection in series-parallel technology：The material preparation of two kinds of spectral absorption complementations is utilized respectively into two
Independent battery prepares multijunction cell by technology in series or in parallel, realizes the effect that enhanced spectrum absorbs.On however,
Stating material blending in the first compound photoactive layer technical method needs accurate control mixed proportion, otherwise due to different materials point
Sub- energy level interferes with each other, and eventually leads to device performance variation；And second of lamination multijunction cell technology is then to front and rear each junction battery
It is more demanding, need carrier quantity and transmission balance matching, and laminated cell preparation process is complicated.
Invention content
The purpose of the present invention is to provide a kind of electrooptical device containing spectral sensitization layer, to improve device to the sun
The absorbability of energy spectrum improves utilization ratio of the device to solar spectral.
To achieve the above object, the present invention provides following technical solution：
The embodiment of the present application discloses a kind of electrooptical device, including：
Hearth electrode；
Top electrode；
Photoactive layer between the hearth electrode and top electrode；
Absorption spectrum and institute between the hearth electrode and photoactive layer, and/or the top electrode and photoactive layer
State the spectral sensitization layer of photoactive layer complementation.
As a further improvement on the present invention, the photoactive layer is by organic conjugate electron donor material and electron acceptor material
Material blending composition, the organic conjugate electron donor material includes conjugatd polymers and organic conjugate oligomer, described
Electron acceptor material include fullerene derivate and organic molecule electron acceptor material.
As a further improvement on the present invention, the material of the photoactive layer is PBDT-TT-F:PCBM（Benzene thiophene-
The film to be formed is blended with fullerene derivate in fluoro thiophene bithiophene copolymer）, the material of the spectral sensitization layer is P3HT（It is poly-
(3- hexyl thiophenes)）.
As a further improvement on the present invention, the spectral sensitization layer is conjugatd polymers or organic conjugate oligomerization
Object.
As a further improvement on the present invention, the conjugatd polymers are selected from by thiophene, fluorenes, carbazole, pyrrolo-
The homopolymerization that one or more units and derived units in pyrroledione, diazosulfide, benzene thiophene, thiophene bithiophene are formed
Object or copolymer.
As a further improvement on the present invention, the organic conjugate oligomer is selected from linear oligo-thiophenes, functionalized modification
It is one or more in oligo-thiophenes, the oligo-thiophenes of branched structure, conjugated organic molecule dyestuff.
As a further improvement on the present invention, the surface of the hearth electrode and/or top electrode is also modified with electrode modification layer,
The material of the electrode modification layer is selected from the salt of organic polymer, metal oxide or alkali metal, and the organic polymer is selected from
Poly- 3,4- ethylenedioxy thiophenes:Poly styrene sulfonate（PEDOT:PSS）It is or one or more in conjugated polymer electrolyte；
The metal oxide is selected from the oxide or nickel of titanyl compound, the oxide of zinc, the oxide of vanadium, the oxide of molybdenum, tungsten
Oxide in it is one or more；The one kind or more of the salt of the alkali metal in lithium fluoride, cesium carbonate, lithium benzoate
Kind.
Compared with prior art, the application chooses and inhales after a kind of polymer material for photoactive layer is had selected
Receiving spectrum has another organic material of complementary performance, by spin coating or other thin film deposition processes, is deposited onto
Between electrode and photoactive layer.This layer of spectral sensitization film can absorb the nonabsorbable solar spectrum of photoactive layer institute, from
And collecting efficiency of the device to solar spectrum can be improved, improve the opto-electronic conversion performance of device.
Description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, to embodiment or it will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments described in application, for those of ordinary skill in the art, without creative efforts,
It can also be obtained according to these attached drawings other attached drawings.
Fig. 1 show the structure diagram of electrooptical device in first embodiment of the invention；
Fig. 2 show the structure diagram of electrooptical device in second embodiment of the invention；
Fig. 3 show the structure diagram of electrooptical device in third embodiment of the invention；
Fig. 4 show the structure diagram of electrooptical device in preferred embodiment；
Fig. 5 show the chemical structural formula of P3HT, PBDT-TT-F and PCBM；
Fig. 6 show the spectral absorption characteristics of P3HT and PBDT-TT-F films；
Fig. 7 is that have the device of spectral sensitization layer compared with the EQE of the device without spectral sensitization layer.
Specific embodiment
In order to overcome the shortcomings that insufficient to the light absorption of certain wave bands in existing organic photoelectric switching device, the present invention uses
By adding in one layer of independent spectral sensitization layer in the devices, to improve absorbability of the device to solar spectral, device is improved
Part is to the utilization ratio of solar spectral.
The embodiment of the invention discloses a kind of electrooptical device, including：
Hearth electrode；
Top electrode；
Photoactive layer between the hearth electrode and top electrode；
Absorption spectrum and institute between the hearth electrode and photoactive layer, and/or the top electrode and photoactive layer
State the spectral sensitization layer of photoactive layer complementation.
Above-mentioned electrooptical device is preferably solar cell, or photomultiplier, photoelectric detector etc. its
Its device.
Absorption spectrum has complementarity between spectral sensitization layer and photoactive layer used in the present invention, and it includes following three layers to contain
Justice：
1st, the material being used to prepare in the material and photoactive layer of spectral sensitization layer cannot be same material, so that light
Spectrum increases the absorption bands for feeling layer and the absorption bands of photoactive layer are misaligned；
2nd, spectral sensitization layer can be with the shorter spectral band of the main absorbing wavelength of absorptance photoactive layer；
3rd, spectral sensitization layer can be with the longer spectral band of the main absorbing wavelength of absorptance photoactive layer.
The position of spectral sensitization layer includes three kinds：
Join shown in Fig. 1, in the first embodiment, spectral sensitization layer 50 is between hearth electrode 20 and photoactive layer 30.Tool
Body, electrooptical device includes transparent substrates 10 and the hearth electrode 20, the spectral sensitization that are respectively formed in transparent substrates 10
Layer 50, photoactive layer 30 and top electrode 40.
Join shown in Fig. 2, in a second embodiment, spectral sensitization layer 50 is between top electrode 40 and photoactive layer 30.Tool
Body, electrooptical device includes transparent substrates 10 and the hearth electrode 20, the photoactive layer that are respectively formed in transparent substrates 10
30th, spectral sensitization layer 50 and top electrode 40.
Join shown in Fig. 3, in the third embodiment, spectral sensitization layer 50 includes first and increases the sense increasing sense layer 52 of layer 51 and second,
Respectively between hearth electrode 20 and photoactive layer 30 and top electrode 40 and photoactive layer 30 specifically, electrooptical device
Including transparent substrates 10 and the hearth electrode being respectively formed in transparent substrates 10 20, first increase sense layer 51, photoactive layer 30,
Second increases sense layer 52 and top electrode 40.
In any one device architecture of above-mentioned three kinds of embodiments, spectral sensitization layer has been involved in the charge transmission of device
Process.
In above-mentioned electrooptical device, hearth electrode is preferably transparent conductive electrode, can be indium tin oxide transparent
Electrode, the tin oxide transparent electrode of Fluorin doped, organic conductive polymer electrode, organic polymer/metal composite electrode；Top electrode
The grid electrode formed for metal electrode or by metal, preferably metal are aluminium, silver, magnesium or gold.
For further smooth electrode surface, while the work(for adjusting electrode is contained, and reduces charge in interelectrode injection barrier,
The surface of hearth electrode can also be modified with electrode modification layer.Electrode modification layer can be aoxidized by organic conductive polymer or metal
The salt of object or alkali metal.Wherein organic polymer decorative layer includes poly- 3,4- ethylenedioxy thiophenes：Poly styrene sulfonate layer or
Conjugated polymer electrolyte layer；Modified metal oxide layer includes：The oxide of zinc, titanyl compound, the oxide of vanadium, molybdenum
Oxide, the oxide of tungsten, nickel oxide；The salt of the alkali metal in lithium fluoride, cesium carbonate, lithium benzoate one
Kind is a variety of
For further smooth electrode surface, while the work(for adjusting electrode is contained, and reduces charge in interelectrode injection barrier,
The surface of top electrode can also be modified with electrode modification layer.Electrode modification layer can be aoxidized by organic conductive polymer or metal
The salt of object or alkali metal.Wherein organic polymer decorative layer includes poly- 3,4- ethylenedioxy thiophenes：Poly styrene sulfonate layer or
Conjugated polymer electrolyte layer；Modified metal oxide layer includes：The oxide of zinc, titanyl compound, the oxide of vanadium, molybdenum
Oxide, the oxide of tungsten, nickel oxide；The salt of the alkali metal in lithium fluoride, cesium carbonate, lithium benzoate one
Kind is a variety of.
In above-mentioned electrooptical device, photoactive layer is total to by organic conjugate electron donor material with electron acceptor material
Mixed composition.Organic conjugate electron donor material includes conjugatd polymers and organic conjugate oligomer, electron acceptor material packet
Include fullerene derivate and organic molecule electron acceptor material.Wherein, conjugatd polymers are by thiophene, fluorenes, carbazole, pyrrole
Cough up what one or more units and derived units in simultaneously pyrroledione, diazosulfide, benzene thiophene, thiophene bithiophene were formed
Homopolymer or copolymer；Organic conjugate oligomer is linear oligo-thiophenes, the oligomerization of functionalized modification oligo-thiophenes, branched structure
It is one or more in thiophene, conjugated organic molecule dyestuff.Fullerene derivate is C60, C70And its corresponding derivative is such as：
PC61BM, PC71BM, ICBA；Organic molecule electron acceptor unit is naphthalimide（NDI）, acid imide（PDI）It is and its derivative
Object.
In above-mentioned electrooptical device, spectral sensitization layer includes conjugatd polymers or organic conjugate oligomerization
Object.The conjugatd polymers are selected from by thiophene, fluorenes, carbazole, pyrrolo-pyrrole-dione, diazosulfide, two thiophene of benzo
The homopolymer or copolymer that one or more units and derived units in fen, thiophene bithiophene are formed；The organic conjugate
Oligomer is in linear oligo-thiophenes, functionalized modification oligo-thiophenes, the oligo-thiophenes of branched structure, conjugated organic molecule dyestuff
In it is one or more.
In the embodiment of the present invention, spectral sensitization layer material used is different materials from photoactive layer material, they
Spectral absorption differ, and complementary with certain spectrum, can realize the extension of spectral response ability.
The embodiment of the invention discloses a kind of electrooptical devices.Those skilled in the art can use for reference present disclosure, fit
When modified technique parameter is realized.In particular, it should be pointed out that all similar substitutions and modifications are for a person skilled in the art
It is it will be apparent that they are considered as being included in the present invention.The application of the present invention is retouched by preferred embodiment
It states, related personnel can significantly not depart from the content of present invention, application as described herein is being modified or fitted in spirit and scope
When change is with combining, to realize and using the technology of the present invention.
For a further understanding of the present invention, the following describes the present invention in detail with reference to examples.
Join shown in Fig. 4, in preferred embodiment, electrooptical device includes transparent substrates 10 and respectively shape
It is modified into hearth electrode 20, hearth electrode decorative layer 60, spectral sensitization layer 50, photoactive layer 30, the top electrode in transparent substrates 10
Layer 70 and top electrode 40.Wherein, hearth electrode 20 uses tin indium oxide transparent conductive glass（ITO）, outer addition polymerization 3,4- enedioxies
Thiophene:Poly styrene sulfonate（PEDOT:PSS）As electrode modification layer 60；It is poly-（3- hexyl thiophenes）（P3HT）For spectral sensitization
Layer 50；PBDT-TT-F and PC61BM blend films are as photoactive layer 30；Aluminium is as top electrode 40, and in 30 He of photoactive layer
Contain LiF between top electrode 40 as metal electrode decorative layer 70.
Fig. 5 show P3HT, PBDT-TT-F and PC61The chemical structural formula of BM.
Fig. 6 show the spectral absorption characteristics of P3HT and PBDT-TT-F films, there it can be seen that P3HT films with
The absorption spectrum of PBDT-TT-F films is different.The film absorption wavelength of PBDT-TT-F is mainly in 550-720 nm, the suction of P3HT
Receipts are predominantly located at 450-600 nm.P3HT films can make up spectral absorption of the PBDT-TT-F films at 450-600 nm
It is insufficient.
The preparation process of electrooptical device shown in Fig. 4 is as follows：
10 mg P3HT are dissolved in 1 mL chlorobenzenes by the configuration of solution, stir 12 hours in an inert atmosphere.By 5.0 mg
PBDT-TT-F and 7.5 mg PC611, the 8- diiodo-octanes of BM and 15 μ L are dissolved in 1,1, the 2- trichloroethanes of 1 mL, in inertia
12 hours of closed stirring in atmosphere.Using spin coating proceeding, in the ito glass on piece cleaned up, one layer of PEDOT of spin coating:
PSS, and 120 DEG C of dryings 10 minutes, then drop in dried PEDOT by P3HT chlorobenzene solutions:It is every with 600 turns on PSS films
The speed spin coating of minute 1 minute.The 120 DEG C of annealing of P3HT films are dried after ten minutes, are revolved with 600 rpms of speed
Apply one layer of PBDT-TT-F and PC61The solution of BM, spin-coating time are 1 minute.Then device is moved on in vacuum coating equipment cavity,
It is evacuated to 5 × 10-4Pa hereinafter, plate the aluminium (Al) of one layer of 100 nm thickness again after the lithium fluoride (LiF) of one layer of 1 nm thickness of plating.
Join shown in Fig. 7, to the device with spectral sensitization layer（Device shown in Fig. 4）With the device without spectral sensitization layer
The EQE of part compares, other than increasing spectral sensitization layer, other technological process all sames.From EQE as can be seen that profit
By the use of P3HT as the electrooptical device of spectral sensitization layer, the less device of spectral sensitization layer has significantly at 400-500 nm
Enhancing, realize the effect of spectral sensitization.The photoelectric current of device is from 11.42 mA/cm2It is increased to 12.16 mA/cm2, reach
6% raising.
In conclusion in solution designed by the present invention, spectral sensitization layer is between electrode and photoactive layer, light
Spectrum increases sense layer with having spectral absorption complementation performance between photoactive film, can improve responding ability of the device to spectrum, together
When spectral sensitization layer participate in the transmission process of charge in device.In solution designed by the present invention, device preparation technology letter
It is single.Meanwhile the structure can make up the shortcomings that photoactive layer is insufficient to certain wave spectrum energy absorptions, improve photoelectric converter
The spectral response range of part, the final electric current output for promoting device.
It should be noted that herein, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any this practical relationship or sequence.Moreover, term " comprising ", "comprising" or its any other variant are intended to
Non-exclusive inclusion, so that process, method, article or equipment including a series of elements not only will including those
Element, but also including other elements that are not explicitly listed or further include as this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
Also there are other identical elements in process, method, article or equipment including the element.
The above is only the specific embodiment of the application, it is noted that for the ordinary skill people of the art
For member, under the premise of the application principle is not departed from, several improvements and modifications can also be made, these improvements and modifications also should
It is considered as the protection domain of the application.
Claims (3)
1. a kind of organic photoelectric switching device, which is characterized in that including：
Hearth electrode；
Top electrode；
The organic photoactive layer being spin-coated between the hearth electrode and top electrode；
The absorption light being spin-coated between the hearth electrode and organic photoactive layer, and/or the top electrode and organic photoactive layer
Spectrum and organic spectral sensitization layer of organic photoactive layer complementation；Wherein,
The material of the organic photoactive layer is PBDT-TT-F:PCBM, the material of organic spectral sensitization layer is P3HT.
2. organic photoelectric switching device according to claim 1, it is characterised in that：The hearth electrode and/or top electrode
Surface is also modified with electrode modification layer, and the material of the electrode modification layer is selected from organic polymer, metal oxide or alkali metal
Salt, the organic polymer be selected from conjugated polymer electrolyte；The metal oxide is selected from the oxidation of titanyl compound, zinc
Object, the oxide of vanadium, the oxide of molybdenum, the oxide of tungsten or nickel oxide in it is one or more；The alkali metal
Salt be selected from lithium fluoride, cesium carbonate, lithium benzoate it is one or more.
3. organic photoelectric switching device according to claim 2, it is characterised in that：The organic polymer is poly- 3,4- second
Support dioxy thiophene:Poly styrene sulfonate.
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| A review of polymer multijunction solar cells;Mahbube Khoda Siddiki, et al.;《Energy & Environmental Science》;20100604;第3卷;page 867–883 * |
| Liquid Crystalline Polymers for Efficient Bilayer-Bulk-Heterojunction Solar Cells;Qingjiang Sun, et al.;《J. Phys. Chem. C》;20090410;第113卷(第18期);page 7892–7897 * |
| Polymer Bulk Heterojunction Photovoltaic Devices with Multilayer Structures Prepared by Thermal Lamination;Motoshi Nakamura, et al.;《ACS APPLIED MATERIALS & INTERFACES》;20091207;第1卷(第2期);page 2703–2706 * |
| Simple tandem organic photovoltaic cells for improved energy conversion efficiency;Chunfu Zhang, et al.;《APPLIED PHYSICS LETTERS》;20080228;第92卷;page 083310 * |
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