CN102024906B - Organic solar cell structure based on oxide doped organic material - Google Patents
Organic solar cell structure based on oxide doped organic material Download PDFInfo
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Abstract
The invention relates to the technical field of an organic photoelectric device and discloses an organic solar cell structure based on oxide doped organic material. The structure comprises a transparent substrate, an anode deposited on the substrate, a buffer layer deposited on the anode, an organic electronic donor layer deposited on the buffer layer, an organic electronic acceptor layer deposited on the organic electronic donor layer and a cathode deposited on the organic electronic acceptor layer in turn from bottom to top. The anode adopts ITO (indium tin oxides) or FTO (fluorine doped tin oxide); the buffer layer adopts the oxide doped organic material, wherein the oxide adopts low-temperature materials such as MoO3 and ReO3; the organic electronic donor layer adopts CuPc or ZnPc; the organic electronic acceptor layer adopts C60 or PTCDA or PTCBI; and the cathode adopts aluminum or magnesium-silver alloy. Each layer, except the anode and cathode, is prepared by various organic film depositing methods such as vacuum evaporation, spraying and printing. Through the invention, the stability of the organic solar cell can be improved.
Description
Technical field
The present invention relates to the organic electro-optic device technical field; Be specifically related to a kind of organic solar energy cell structure based on oxide-doped organic material; This structure adopts the doped metallic oxide organic material as resilient coating, under the prerequisite of the energy conversion efficiency that does not reduce organic solar batteries, improves the stability of battery.
Background technology
At present, the solar battery product on the market is main with inorganic material, mainly is based on semi-conducting materials such as silicon wafer, cadmium telluride and III-V compounds of group.This type battery performance is stable, and the life-span is long, but cost of manufacture is high, complex process, and material requirements is harsh, and might cause follow-up pollution, makes this type solar cell large tracts of land to promote.Organic solar batteries material therefor wide material sources, cheap, preparation technology is simple, be prone to obtain large tracts of land, makes that reducing the battery cost becomes possibility, and can adopt flexible substrate, be easy to carry.
The reason that the energy conversion efficiency of organic solar batteries is low is the fundamental property of battery operated principle and organic semiconducting materials.After illumination was mapped to organic solar batteries, photon was absorbed by organic semiconductor layer, and excitation electron forms electron hole pair (exciton) from the valence to the conduction band.These excitons only are diffused into the p-n junction place that is made up of p type material and n type material just can separate into charge carrier freely, and the exciton diffusion length of organic material has only about 10nm, so the exciton at 20nm place could separate around only at the donor-receiver interface.In addition, the carrier mobility of organic material is very low, generally 10
-8～10
-2Cm
2Between/the Vs, charge carrier is prone to take place compound or caught by trap in transport process.
In decades in the past, researcher has been carried out a large amount of work, and double-deck heterojunction device, body heterojunction device, the micromolecule device that mixes vapor deposition and the research of hybrid device have all had considerable progress.At present, the efficient of organic dye sensitized nanocrystalline battery surpasses 10%, and the organic molecule solar battery efficiency has reached 5% in the laboratory.According to simulation and forecast, in the device that the band system and the mobility of the level structure of device, material all is optimized, the efficient of body heterojunction polymer/fullerene solar cell can reach 11%, and the efficient of cascade device can reach 16%.
Except that battery efficiency, another important indicator of weighing solar cell properties is that the life-span of battery is promptly stable.Generally believe that after the conversion efficiency of solar cell surpassed 10%, reaches 10000 hours useful life simultaneously, this technology will be used at faster speed.From conversion efficiency and useful life, even the best organic solar batteries of present performance, also only have several thousand hours useful life.The instability of organic solar batteries mainly be because influence, electrode material and the organic material less stable of external environment and electrode and organic film at the interface interaction.For the influence of external environment, adopt encapsulation technology usually, the oxygen in the blocks air, hydrone get in the device and react with film.Interface that it should be noted that electrode and organic film is very big to the influence of device lifetime.For example, ito glass is a frequent adopted anode in the organic semiconductor device, and the In in the ito thin film penetrates into and changes its material behavior in the organic film, is a major reason that reduces device stability.
Summary of the invention
The technical problem that (one) will solve
In view of this; Main purpose of the present invention is to provide a kind of organic solar energy cell structure based on oxide-doped organic material; With under the prerequisite of the energy conversion efficiency that does not reduce organic solar batteries, improve the not stability of the organic solar batteries of encapsulation.
(2) technical scheme
For achieving the above object, the invention provides a kind of organic solar energy cell structure based on oxide-doped organic material, this structure comprises from the bottom to top successively:
Transparent substrates;
Be deposited on the anode on this substrate;
Be deposited on the resilient coating on this anode;
Be deposited on the organic electronic donor layer on this resilient coating;
Be deposited on the organic electronic receptive layers on this organic electronic donor layer; And
Be deposited on the negative electrode on this organic electronic receptive layers.
In the such scheme, said anode is ITO or FTO.
In the such scheme, this structure also comprises modifies to improve the decorative material of the carrier transport between anode and the resilient coating said anode, and this decorative material adopts nickel or golden Au.
In the such scheme, said resilient coating is made up of oxide-doped organic material.
In the such scheme, the oxide in the said resilient coating adopts MoO
3, ReO
3Or WO
3
In the such scheme, the organic material in the said resilient coating adopts CuPc or ZnPc.
In the such scheme, oxide and organic material are when mixing in the said resilient coating, and the growth rate ratio is between 1: 10 to 1: 1.
In the such scheme, said organic electronic donor layer adopts CuPc or ZnPc.
In the such scheme, said organic electronic receptive layers adopts C60 and derivative, PTCDA or PTCBI.
In the such scheme, said negative electrode adopts aluminium Al or magnesium silver alloy.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
Organic solar energy cell structure based on oxide-doped organic material provided by the invention; Through introducing the resilient coating that mixes; With improving organic interface topography of giving between body layer and the anode; Reduce In in the ito anode simultaneously to the infiltration of organic material, and then can improve the stability of organic solar batteries.
Description of drawings
Fig. 1 is the sketch map of the organic solar energy cell structure based on oxide-doped organic material provided by the invention;
Fig. 2 is the I-V curve of the organic solar energy cell structure based on oxide-doped organic material provided by the invention; Wherein normal component refers to the ITO/CuPc/C60/Al device, and structure devices of the present invention is ITO/MoO
3: CuPc/CuPc/C60/Al device, light source are 100mW/cm
2The simulated light of AM1.5;
Fig. 3 is the efficient curve over time of normal component and structure devices of the present invention, and test is under atmospheric environment, to carry out, and device does not encapsulate.
Embodiment
For making the object of the invention, technical scheme and advantage clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, to further explain of the present invention.
See also shown in Figure 1ly, Fig. 1 is the sketch map of the organic solar energy cell structure based on oxide-doped organic material provided by the invention, and this structure comprises from the bottom to top successively:
One transparent substrates 10 can adopt the good flexible polymer of glass or light transmission;
One anode 20, this anode 20 is deposited on the substrate 10, and this anode can be following arbitrary material: ITO, FTO, or with the ITO or the FTO of high-work-function metal modifications such as gold or nickel;
One resilient coating 30, this resilient coating 30 is deposited on the anode 20, is made up of oxide-doped organic material; Arbitrary material: MoO below oxide can be selected
3, ReO
3, WO
3Arbitrary material: CuPc, ZnPc below organic material can be selected; In this resilient coating 30 during the doping of oxide and organic material the growth rate ratio be between 1: 10 to 1: 1;
One organic electronic donor layer 40, this organic electronic donor layer 40 is deposited on the resilient coating 30, arbitrary material: CuPc, ZnPc below can selecting;
One organic electronic receptive layers 50, this organic electronic receptive layers 50 is deposited on the organic electronic donor layer 40, arbitrary material: C60 and derivative thereof, PTCDA, PTCBI below can selecting; And
One negative electrode 60, this negative electrode 60 is deposited on the organic electronic receptive layers 50, arbitrary material below can selecting: aluminium Al, magnesium silver alloy.
The present invention is to provide a kind of organic solar energy cell structure that improves organic solar batteries stability; Related is a kind of organic solar energy cell structure that uses the doped metallic oxide organic material as anode buffer layer; As shown in Figure 1, this structure is made up of transparent substrates 10, anode 20, resilient coating 30, electron donor layer 40, electron acceptor layer 50 and negative electrode 60 from the bottom to top successively.
In the present invention, transparent substrates 10 can adopt glass or the good flexible polymer of light transmission, and light gets into device from this substrate 10.
In the present invention, anode 20 is deposited on the substrate 10, and this anode can be following arbitrary material: ITO, FTO, or with the ITO or the FTO of high-work-function metal modifications such as gold or nickel.
In the present invention, to such an extent as to resilient coating 30 be meant can be smoothly, parent's profit anode surface, energy level coupling can fine realization hole transport composite organic-inorganic material, can adopt inorganic material is the low-temperature metal oxide, arbitrary material: MoO below can selecting
3, ReO
3, WO
3, organic material can be selected CuPc or ZnPc.In this resilient coating 30 during the doping of oxide and organic material the growth rate ratio be between 1: 10 to 1: 1.
In the present invention; Organic electronic donor layer 40 is a light absorbing zone with organic electronic receptive layers 50; Exciton separates the formation free carrier at the interface at both; Give the LUMO and LUMO and the HOMO energy level that the HOMO energy level must be higher than acceptor respectively of body, and must be greater than 0.4eV to the difference of the LUMO of body and acceptor and HOMO energy level.In addition, organic electronic donor layer 40 should mate with the HOMO energy level of the resilient coating that mixes, and can adopt CuPc or ZnPc; Arbitrary material: C60 and derivative thereof, PTCDA, PTCBI below organic electronic receptive layers 50 can be selected.
In the present invention, negative electrode 60 can adopt aluminium or magnesium silver alloy.
Among the present invention, except anode and negative electrode, all the other each layers can adopt the method for various deposition organic membrane such as vacuum evaporation, spin coating, printing to prepare.Resilient coating is (like MoO
3Doped with Cu Pc) realization can adopt coevaporation technology or with oxide and organic material be dissolved in altogether with a kind of solvent then the method for spin coating or printing realize.
Through the resilient coating that introduce to mix, with improving organic interface topography of giving between body layer and the anode, reduce In in the ito anode simultaneously to the infiltration of organic material, can improve the stability of organic solar batteries.
The organic solar energy cell structure that the present invention proposes, the fill factor, curve factor of battery increases, and energy conversion efficiency slightly improves.Table 1 is that the performance of normal component and device of the present invention compares.The stable comparison with standard device architecture of the device (see figure 3) that improves.
Table 1
Below in conjunction with embodiment the present invention is specifically described, but the present invention is not limited only to cited embodiment.
Growth for solar battery on the ito glass substrate that cleans up, the about 150nm of ITO thickness, about 20 Ω of square resistance/.Adopt OMBD equipment (OMBD) growth organic film and negative electrode, vacuum is about 4 * 10 during growth
-7Torr.The organic film growth rate approximately
Metal A l growth rate approximately
The about 0.5mm of the effective area of battery
2Xenon lamp is the solar energy analog light source, and light intensity is 100mW/cm
2, the I-V curve is measured with Keithley2400, and all tests all are under atmospheric environment, to carry out.
Device architecture is: normal component ITO/CuPc 40nm/C6050nm/Al, structure devices ITO/MoO of the present invention
3: CuPc (1: 10) 10nm/CuPc 30nm/C6050nm/Al.
The I-V curve of device under light conditions is as shown in Figure 2, and device efficiency is as shown in Figure 3 over time.In air, place after 30 minutes, it is initial 63% that the efficient of normal component is reduced to, and the efficient of device of the present invention is initial 80%, and the stability of device improves.
The implication of relevant abbreviation title is following among this paper:
ITO: indium tin oxide
MoO
3: molybdenum oxide
ReO
3: rheium oxide
WO
3: tungsten oxide
CuPc: CuPc (Copper phthalocyanine)
ZnPc: Phthalocyanine Zinc (Zinc phthalocyanine)
C60: fullerene (fulleren)
PTCDA: perylene tetracarboxylic acid dianhydride (3,4,9,10-perylene tetracarboxylic)
PTCBI: bisbenzimidazole generation-3,4,9,10-tetracarboxylic acid Ji perylene (3,4,9,10-perylenetetracarboxylic bis-benzimidazole)
HOMO: the sub-occupied orbital of best result
LUMO: minimum molecule is occupied orbital not
Above-described specific embodiment; The object of the invention, technical scheme and beneficial effect have been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the organic solar energy cell structure based on oxide-doped organic material is characterized in that, this structure comprises from the bottom to top successively:
Transparent substrates;
Be deposited on the anode on this substrate;
Be deposited on the resilient coating on this anode;
Be deposited on the organic electronic donor layer on this resilient coating;
Be deposited on the organic electronic receptive layers on this organic electronic donor layer; And
Be deposited on the negative electrode on this organic electronic receptive layers;
Wherein, said resilient coating is made up of oxide-doped organic material, and said oxide adopts MoO
3, ReO
3Or WO
3, said organic material adopts CuPc or ZnPc, and oxide and organic material are when mixing in the said resilient coating, and the growth rate ratio is between 1: 10 to 1: 1.
2. the organic solar energy cell structure based on oxide-doped organic material according to claim 1 is characterized in that, said anode is ITO or FTO.
3. the organic solar energy cell structure based on oxide-doped organic material according to claim 1; It is characterized in that; This structure also comprises modifies to improve the decorative material of the carrier transport between anode and the resilient coating said anode, and this decorative material adopts nickel or golden Au.
4. the organic solar energy cell structure based on oxide-doped organic material according to claim 1 is characterized in that, said organic electronic donor layer adopts CuPc or ZnPc.
5. the organic solar energy cell structure based on oxide-doped organic material according to claim 1 is characterized in that, said organic electronic receptive layers adopts C60 and derivative, PTCDA or PTCBI.
6. the organic solar energy cell structure based on oxide-doped organic material according to claim 1 is characterized in that, said negative electrode adopts aluminium Al or magnesium silver alloy.
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| CN102569654B (en) * | 2012-01-13 | 2015-05-13 | 暨南大学 | Organic solar cell doped with phosphorescent dye |
| CN102623641A (en) * | 2012-03-27 | 2012-08-01 | 华北电力大学 | Polymer solar anode modifying battery and preparation method thereof |
| CN102610759A (en) * | 2012-03-30 | 2012-07-25 | 中国科学院长春应用化学研究所 | Conjugated thin polymer film solar cell and method for producing same |
| CN103422056A (en) * | 2012-05-14 | 2013-12-04 | 海洋王照明科技股份有限公司 | Conductive thin film, and preparation method and application thereof |
| CN103824946A (en) * | 2012-11-19 | 2014-05-28 | 海洋王照明科技股份有限公司 | Polymer solar cell and preparation method thereof |
| CN104051660A (en) * | 2013-03-12 | 2014-09-17 | 海洋王照明科技股份有限公司 | Composite anode and manufacturing method thereof, and organic electroluminescent device and manufacturing method thereof |
| CN105493304B (en) * | 2013-08-06 | 2020-01-31 | 新南创新私人有限公司 | High efficiency stacked solar cells |
| CN114921804B (en) * | 2022-04-26 | 2023-06-20 | 华南理工大学 | InN/organic heterostructure-based photoelectrode material and preparation method and application thereof |
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| CN1617355A (en) * | 2004-12-09 | 2005-05-18 | 复旦大学 | Novel organic solar energy cell structure and its preparing method |
| CN1719956A (en) * | 2004-07-08 | 2006-01-11 | 城户淳二 | Organic devices, organic electroluminescent devices and organic solar cells |
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| CN1719956A (en) * | 2004-07-08 | 2006-01-11 | 城户淳二 | Organic devices, organic electroluminescent devices and organic solar cells |
| CN1617355A (en) * | 2004-12-09 | 2005-05-18 | 复旦大学 | Novel organic solar energy cell structure and its preparing method |
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