CN107123737B - Undoped high efficiency organic photovoltaic cells - Google Patents
Undoped high efficiency organic photovoltaic cells Download PDFInfo
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- CN107123737B CN107123737B CN201710301803.4A CN201710301803A CN107123737B CN 107123737 B CN107123737 B CN 107123737B CN 201710301803 A CN201710301803 A CN 201710301803A CN 107123737 B CN107123737 B CN 107123737B
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Abstract
The invention discloses a kind of undoped high efficiency organic photovoltaic cells, including transparent insulating substrate, transparent anode electrode layer, anode modification layer, hypothallus, cathodic modification layer, the negative electrode layer to be formed are stacked gradually on transparent insulating substrate, and several splitting layers being arranged in hypothallus are formed.The splitting layer provides several dissociation interfaces for exciton, can effectively improve the energy conversion efficiency of organic solar batteries.
Description
Technical field
The invention belongs to electrooptical device technical fields, particularly relate to a kind of undoped high efficiency organic photovoltaic
Battery.
Background technique
The research of organic solar batteries starts from 1958, and Kearns and Calvin are by magnesium phthalocyanine dye
(MgPc) it is clipped between the electrode of two different work functions, " sandwich " structure is made, to obtain the open circuit of 200 mV
Voltage, but the output of its short circuit current is then very low, so its energy conversion efficiency is relatively low.This organic sun of single layer
Energy battery structure was substituted using double layer heterojunction structure by C.W.Tang in 1986, has obtained 1% energy turn
Change efficiency.The reason of energy conversion efficiency is increased dramatically is to think that double layer heterojunction structure provides an efficient exciton
The interface of fractionation, in other words double layer heterojunction structure, which makes neutral electron-hole pair split into free carrier, becomes more
Be easy.But due to only existing a heterojunction boundary in two-layered medium structure battery, and it common are the exciton of machine material
Diffusion length is shorter, is much smaller than its optical absorption length, those light-generated excitons far from heterojunction boundary can not dissociate to be formed
Photoelectric current, which greatly limits the energy conversion efficiencies of organic photovoltaic battery.For this purpose, people be developed based on two kinds it is material doped
Give acceptor heterojunction device architecture.Bulk heterojunction structure considerably increases the interface of hetero-junctions, can effectively facilitate exciton
Dissociation, but the structure of battery is also more complicated.Meanwhile the performance of battery is influenced by two kinds of mixed proportions to acceptor material
It is larger, it needs accurately to control the doping ratio of donor or receptor, increases the difficulty of device preparation, be unfavorable for large-scale work
Industry metaplasia produces.The present invention seeks to overcome in background technique exciton fission interface in double layer heterojunction structure organic photovoltaic battery
Few, battery efficiency is low and the problem of mixture heterojunction structure battery device preparation process complexity, proposes that novel non-of one kind is mixed
Miscellaneous high efficiency organic photovoltaic cells.
Summary of the invention
In order to overcome the deficiencies in the prior art in background technique, the purpose of the present invention is to provide a kind of undoped high efficiency
Organic photovoltaic battery is provided with splitting layer in the photovoltaic cell, increases exciton fission interface, while avoiding complicated doping
Technique.
In order to achieve the above-mentioned object of the invention, technical scheme is as follows:
A kind of undoped high efficiency organic photovoltaic cells, it is characterised in that the undoped high efficiency organic photovoltaic electricity
Pond, including transparent insulating substrate, stacked gradually on transparent insulating substrate the transparent anode electrode layer to be formed, anode modification layer,
Hypothallus, cathodic modification layer, negative electrode layer, and be arranged in hypothallus first splitting layer, second splitting layer,, N
Splitting layer (N is the integer more than or equal to 1) is formed；Described every layer of the layer of splitting with a thickness of 2~5 nm；Described first is split
Distance of the parting apart from anode modification layer is greater than 5 nm；Distance of the N decorative layer apart from cathodic modification layer is greater than 5 nm；
The distance of adjacent splitting layer is greater than 5 nm.
Further, the material of the transparent insulating substrate is quartz glass, silicate glass, vagcor, sodium
Lime glass, polyvinyl chloride, polycarbonate or polyester；The transparent insulating substrate with a thickness of 1.1~1.5 mm.
Further, it is tin indium oxide, zinc oxide aluminum, zinc-gallium oxide, oxidation that the transparent anode electrode layer, which is material,
Indium zinc, gold, aluminium, silver or carbon nanotube conductive film；The transparent anode electrode layer with a thickness of 80~120 nm.
Further, the anode modification layer is high work function transparent metal oxide, including MoO3, WoO3, V2O5,
Thickness 2-10 nm.
Further, the hypothallus is fullerene, including C60 and C70,40~100 nm of thickness.
Further, the splitting layer is one or more of TPD, TAPC, CBP, NPB, 2-TNATA.
Further, the cathodic modification layer is BCP, Bphen or LiF, thickness 1-10 nm.
Further, the material of the negative electrode layer is Ag, Al, Ca-Al alloy, Mg-Ag alloy, ITO；It is described
Negative electrode layer with a thickness of 80~120 nm.
Heretofore described splitting thickness degree is very thin, after 2~-5 nm, exciton fission, cleaves between layer and anode
Hole between electronics and splitting layer and cathode, can both be transported by energy level, and can also be crossed and be split by way of Suichuan
Parting, and finally collected by respective electrode.The present invention increases exciton fission by the way that splitting layer is arranged in receiver substrate layer
Interface.As soon as every increase a splitting layer, it will increase two exciton fission interfaces.Compared with traditional double layer heterojunction battery, swash
The dissociation interface of son is increased significantly, improves the energy conversion efficiency of battery.Compared with bulk heterojunction battery, complexity is avoided
Doping process, battery structure is simpler, is suitable for the industrialized production of organic photovoltaic battery.
Detailed description of the invention
Fig. 1 is the undoped high efficiency organic photovoltaic cells structural schematic diagram of the embodiment of the present invention.
Specific embodiment
In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with
Embodiment, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain
The present invention is not intended to limit the present invention.
Referring to Fig. 1, a kind of undoped high efficiency organic photovoltaic cells structural schematic diagram of display inventive embodiments.
A kind of undoped high efficiency organic photovoltaic cells, it is characterised in that the undoped high efficiency organic photovoltaic electricity
Pond, including transparent insulating substrate, stacked gradually on transparent insulating substrate the transparent anode electrode layer to be formed, anode modification layer,
Hypothallus, cathodic modification layer, negative electrode layer, and be arranged in hypothallus first splitting layer, second splitting layer,, N
Splitting layer (N is the integer more than or equal to 1) is formed；Described every layer of the layer of splitting with a thickness of 2~5 nm；Described first is split
Distance of the parting apart from anode modification layer is greater than 5 nm；Distance of the N decorative layer apart from cathodic modification layer is greater than 5 nm；
The distance of adjacent splitting layer is greater than 5 nm.,
The material of above-mentioned transparent insulating substrate is preferably quartz glass, silicate glass, vagcor or soda-lime glass
The equal transparent insulations plastic cement such as transparent glass or polyvinyl chloride (PVC), polycarbonate (PC) or polyester (PET) is thick
Degree is preferably 1.1~1.5 mm.
The material of above-mentioned transparent anode electrode layer is preferably tin indium oxide (ITO), and thickness is preferably 80~200 nm.
Since the transparent anode electrode layer is constituted using transparent conductive material or metallic film, and thickness is thin, therefore can play
The effect of electrode, and the transmission of sunlight is not influenced.The transparent anode electrode layer that is to say undoped high efficiency organic photovoltaic electricity
The anode in pond, and photoetching corrosion method can be used and corroded into stripe, to form stripe electrode.
Above-mentioned anode modification layer is preferably high work function inorganic, metal oxide material, for example, adopt molybdenum trioxide (MoO3),
At least one of tungstic acid (WoO3) or vanadic anhydride (V2O5), the thickness of the anode modification layer is preferably 2~10
nm.Due to anode modification layer, in visible light region almost without light absorption, thus its loss very little to sunlight, it can neglect
Slightly disregard, so most of sunlight is still absorbed by photosensitive layer.The presence of anode modification layer be to transparent anode electrode layer into
Row modification, improves the work function of transparent anode electrode layer.Increase the built in field of battery, promotes electrode to the electronics and sky of dissociation
The collection in cave.
Above-mentioned hypothallus is preferably fullerene, including C60 and C70 etc., and thickness is preferably 40~100 nm.The matrix
Layer generates the main photosensitive region of photoelectric current as light is absorbed, and effect is after photosensitive layer absorbs photon energy, and generation has
Electronics~hole pair of certain binding force, that is, exciton, exciton are in electroneutral.Exciton is in the interface of splitting layer and hypothallus electricity
Be split into free carrier under field action, the free carrier in hypothallus respectively to two drift electrodes, to be formed
Photoelectric current output.
Above-mentioned splitting layer is one or more of TPD, TAPC, CBP, NPB, 2-TNATA.
Above-mentioned cathodic modification layer is BCP, Bphen or LiF, thickness 1-10 nm.
Above-mentioned negative electrode layer by metallic films such as Ag, Al, Ca-Al alloy, Mg-Ag alloys, the negative electrode layer
With a thickness of 80~120nm.The negative electrode layer that is to say the cathode of single layer organic solar batteries.
Why inefficient conventional double organic solar batteries are, the main reason is that the light-generated excitons in battery cannot
Effectively split.Exciton splits this process and occurs mainly at donor and acceptor interface.However in double-deck organic sun
In energy battery, donor~acceptor interface of exciton fractionation is only existed.The overwhelming majority cannot be diffused into the exciton of this interface
It can occur compound, like water off a duck's back for photogenerated current, this is also the lower most important original of the double-deck organic solar batteries efficiency
Cause.Based on this theory, one or more splitting layer is arranged in the present embodiment in hypothallus, increases the interface of exciton fission
Number, provides more exciton fission regions, increases the photoelectric current and energy conversion efficiency of battery.When use C70 as base
When matter layer, the undoped organic photovoltaic battery energy conversion efficiency of the present embodiment is up to 2% or more, and for double-deck organic sun
For energy battery, interface is split due to lacking effective exciton, thus its efficiency is generally all very low, such as existing be not provided with is split
The energy conversion efficiency of the organic solar batteries of parting is below 1%.When using C60 as hypothallus, the present embodiment is non-
Doping organic photovoltaic battery energy conversion efficiency is up to 1% or more, and for the double-deck organic solar batteries, due to lacking
Few effective exciton splits interface, thus its efficiency is generally all very low, is not provided with the energy of the organic solar batteries of splitting layer
Transfer efficiency is measured below 0.5%.For the relatively existing double-deck organic solar batteries, the present embodiment organic solar electricity
The energy conversion efficiency in pond improves significant.
The working principle of the present embodiment single layer organic solar batteries is as follows: when sunlight is mapped to from transparent insulating substrate
Afterwards, since transparent insulating substrate is that transparent, transparent anode electrode layer uses transparent conductive material, while anode modification layer is
It is bright, thus its loss very little to sunlight, can be ignored, therefore, most sunlights through transparent insulating substrate,
Transparent anode electrode layer and electrical field augmentation layer are mapped on hypothallus, and are absorbed by hypothallus, and hypothallus absorbs the light of sunlight
After sub- energy, the electronics~hole pair with certain binding force, that is, exciton are generated.Exciton is away from nearest splitting
The interface of layer and hypothallus is dissociated into free electron and hole, due to existing between transparent anode electrode layer and negative electrode layer
Work function difference, so that the inside of organic solar batteries device generates built in field.Free electron and hole are above-mentioned built-in
It under electric field action, drifts about respectively to transparent anode electrode layer and negative electrode layer in the photo layer, to form photoelectric current output.
Several specific embodiments of the present invention are given below, it should be appreciated that following embodiment is of the invention specifically to answer
With being not intended to limit the present invention.
Embodiment one
Undoped high efficiency organic photovoltaic cells, device architecture are as follows: 1.2 mm/ transparent anode of transparent insulating substrate Glass
200 5 nm/C70 of nm/ anode modification layer MoO3 of electrode layer ITO, 15 nm/ first cleaves 5 nm/ C70 15 of layer TAPC
Nm/ second cleaves 5 nm/ C70 of layer TAPC, 15 nm/ third and cleaves 5 nm/ C70 of layer TAPC, 15 nm/ cathodic modification layer
5 nm/ cathode electrode Al of Bphen, 100 nm, wherein hypothallus is the C70 of 60 nm, cleaves layer there are three settings in battery,
That is N=3 can form 6 organic heterojunction interfaces for exciton fission, the distance of the first splitting layer distance MoO3 anode modification layer
Greater than 5 nm, the distance that third cleaves layer distance Bphen cathodic modification layer is greater than 5 nm, the first splitting layer and the second splitting interlayer
Distance be greater than 5 nm, the second splitting layer and third splitting the distance between layer are greater than 5 nm.
Embodiment two
Undoped high efficiency organic photovoltaic cells, device architecture are as follows: 1.2 mm/ transparent anode of transparent insulating substrate Glass
200 5 nm/C60 of nm/ anode modification layer MoO3 of electrode layer ITO, 10 nm/ first cleaves 2 nm/ C60 of layer NPB, 10 nm/
Second splitting 2 nm/ C60 of layer NPB, 10 nm/ third splitting 2 nm/ C60 of layer NPB, 10 nm/ the 4th cleaves layer NPB 2
10 nm/ cathodic modification layer BCP of nm/ C60,10 nm/ cathode electrode Ag, 80 nm, wherein hypothallus is the C60 of 40 nm, electricity
There are four layer, i.e. N=4 is cleaved in pond, 8 organic heterojunction interfaces can be formed for exciton fission.
Embodiment three
1.2 200 nm/ anode modification layer MoO3 of mm/ transparent anode electrode layer ITO of N=1, Glass, 5 nm/C70 25
Nm/ first cleaves 5 nm/ C70 of layer TPD, 25 nm/ cathodic modification layer BCP, 10 nm/ cathode electrode Ag, 80 nm, wherein base
Matter layer is the C70 of 50 nm, and the TPD that the splitting layer in battery is 5 nm can form 2 organic heterojunction interfaces for exciton solution
From.
Example IV
1.2 200 nm/ anode modification layer MoO3 of mm/ transparent anode electrode layer ITO of N=2, Glass, 5 nm/C60 20
Nm/ first cleaves 2 nm/ C60 of layer CBP, 20 nm/ second and cleaves 2 nm/C60 of layer CBP, 20 nm/ cathodic modification layer BCP
10 nm/ cathode electrode Ag, 80 nm, wherein hypothallus is the C60 layer of 60 nm, and the TPD that the splitting layer in battery is 5 nm has 2
A splitting layer can form 4 organic heterojunction interfaces for exciton fission.
Claims (7)
1. a kind of undoped high efficiency organic photovoltaic cells, it is characterised in that: the undoped high efficiency organic photovoltaic cells,
Including transparent insulating substrate, the transparent anode electrode layer to be formed, anode modification layer, matrix are stacked gradually on transparent insulating substrate
Layer, cathodic modification layer, negative electrode layer, and be arranged in hypothallus the first splitting layer, the second splitting layer ..., N splits
Parting is formed, and N is the integer more than or equal to 1；Described every layer of the layer of splitting with a thickness of 2~5 nm；First splitting
Distance of the layer apart from anode modification layer is greater than 5 nm；Distance of the N splitting layer apart from cathodic modification layer is greater than 5 nm；Phase
The distance of neighbour's splitting layer is greater than 5 nm, and the hypothallus is C60 or C70,40~100 nm of thickness.
2. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, it is characterised in that: described is transparent exhausted
The material of edge substrate is quartz glass, silicate glass, vagcor, soda-lime glass, polyvinyl chloride, polycarbonate or poly-
Ester；The transparent insulating substrate with a thickness of the .5 of 1 .1~1 mm.
3. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, it is characterised in that: the transparent sun
The material of pole electrode layer is tin indium oxide；The transparent anode electrode layer with a thickness of 80~200 nm.
4. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, it is characterised in that: the anode is repaired
Decorations layer is one of molybdenum trioxide, tungstic acid or vanadic anhydride, thickness 2-10 nm.
5. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, which is characterized in that the splitting layer
For one or more of TPD, TAPC, CBP, NPB, 2-TNATA.
6. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, it is characterised in that: the cathode is repaired
Adoring layer is BCP, Bphen or LiF, thickness 1-10 nm.
7. a kind of undoped high efficiency organic photovoltaic cells according to claim 1, it is characterised in that: the cathode electricity
The material of pole layer is Ag, Al, Ca-Al alloy, Mg-Ag alloy, ITO；The negative electrode layer with a thickness of 80~120
nm。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101882664A (en) * | 2010-06-13 | 2010-11-10 | 西南大学 | Organic solar cell with monolayer organic material as functional layer |
| EP2329543A1 (en) * | 2008-09-26 | 2011-06-08 | The Regents of the University of Michigan | Organic tandem solar cells |
| CN103730588A (en) * | 2013-12-31 | 2014-04-16 | 吉林大学 | Laminated organic electroluminescent device based on single-layer light emitting units |
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- 2017-05-02 CN CN201710301803.4A patent/CN107123737B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2329543A1 (en) * | 2008-09-26 | 2011-06-08 | The Regents of the University of Michigan | Organic tandem solar cells |
| CN101882664A (en) * | 2010-06-13 | 2010-11-10 | 西南大学 | Organic solar cell with monolayer organic material as functional layer |
| CN103730588A (en) * | 2013-12-31 | 2014-04-16 | 吉林大学 | Laminated organic electroluminescent device based on single-layer light emitting units |
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