CN103236501A - Metal-halide-doped organic hole transporting layer, and preparation method and application thereof - Google Patents
Metal-halide-doped organic hole transporting layer, and preparation method and application thereof Download PDFInfo
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- CN103236501A CN103236501A CN2013100789253A CN201310078925A CN103236501A CN 103236501 A CN103236501 A CN 103236501A CN 2013100789253 A CN2013100789253 A CN 2013100789253A CN 201310078925 A CN201310078925 A CN 201310078925A CN 103236501 A CN103236501 A CN 103236501A
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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
- Y02E10/542—Dye sensitized solar cells
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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
Abstract
The invention relates to a preparation method of a metal-halide-doped organic hole transporting layer. The preparation method includes: mixing organic hole transporting material and organic solvent to prepare organic hole transporting material solution; mixing metal halide and organic solvent to prepare metal halide dopant solution; mixing the organic hole transporting material solution and the metal halide dopant solution to form mixed solution; and spin-coating a substrate with the mixed solution, and heating and drying to obtain the hole transporting layer. The invention further discloses the organic hole transporting layer prepared by the method, and a solar cell with the organic hole transporting layer. The preparation method is simple. The number of carriers of the prepared organic hole transporting layer is increased, hole mobility and conductivity of the hole transporting layer are increased evidently, energy band position of the hole transporting layer is changed, the hole transporting layer has better photoelectric property, and the hole transporting layer is well applicable to the devices such as dye-sensitized solar cells, organic solar cells, and organic-inorganic hybrid solar cells.
Description
Technical field
The invention belongs to technical field of semiconductor, be specifically related to a kind of preparation method of organic cavity transmission layer, and utilize organic cavity transmission layer and its application in all-solid-state dye-sensitized solar cell of this method preparation.
Background technology
The organic hole semi-conducting material is widely used in fields such as Organic Light Emitting Diode, DSSC, organic solar batteries, field-effect transistors because its particular performances has become more and more welcome.This material can adopt the solution thin films, and technology is simple, and is cheap, shown great potential in the electronic market in future.And can further improve its range of application by this material being mixed to adjust its photoelectric properties, be the main flow direction that future studies are used.
Existing organic cavity transmission layer is based on aromatic series triphenylamine and conduction high polymer, and in order to improve the performance of organic hole transferring material, the main P type dopant that adopts carries out doping treatment at present.P type dopant is mainly simple substance oxygen, iodine, lewis acid, transition metal oxide, organometallic complex etc.Can be from 4.4 * 10 through the film conductivity that this P type mixes
-5Bring up to 5.3 * 10
-4Scm
-1, the photoelectric conversion efficiency of DSSC brings up to 6.1% from 2.6%.Yet this class dopant solubility in organic solvent usually is lower or will adopt the evaporating deposition technique of higher cost, and there is the problem of long-time stability deficiency in it, has limited the application of P type doped layer in organic cavity transmission layer.
Summary of the invention
One of purpose of the present invention provides a kind of preparation method of organic cavity transmission layer of metal halide doping, utilizing metal halide to carry out the P type in this method mixes, the solubility height of dopant, depositing operation is simple and with low cost, prepared organic cavity transmission layer good stability, effective, be used for the photoelectric conversion efficiency that all-solid-state dye-sensitized solar cell can significantly improve battery.
Realize that the concrete technical scheme that this purpose of the present invention adopts is as follows.
The preparation method of the organic cavity transmission layer of doping metal halogenide, comprise the steps: organic hole transferring material and organic solvent are hybridly prepared into organic hole transferring material solution, metal halide and organic solvent are hybridly prepared into the metal halide dopant solution, then organic hole transferring material solution are mixed and fully stir forming mixed solution with the metal halide dopant solution.Mixed solution is spun in the substrate, and heating, drying at a certain temperature, described hole transmission layer namely obtained.
As present invention further optimization, described metal halide be doped to doping content in the organic hole transferring material by mass fraction control between 1% to 50%, preferably 5% to 40%, most preferably be between 5.9% to 25%.
As present invention further optimization, described organic hole transferring material is P3HT, spiro-OMeTAD, and poly-3-octyl group thiophene, P3OT, poly-3,4-enedioxy thiophene, PEDOT, at least a among the TPD.
As present invention further optimization, described machine solvent is at least a in chlorobenzene, dichloro-benzenes, the acetonitrile.
As present invention further optimization, described metal halide is at least a in butter of tin, the Antimony pentachloride.
As present invention further optimization, described bake out temperature is 40 ℃-90 ℃.
As present invention further optimization, described substrate is TiO
2, SnO
2, ZnO, Al
2O
3, monocrystalline silicon, in the polysilicon any one.
Another object of the present invention is to provide a kind of organic cavity transmission layer of utilizing method for preparing.
Another purpose of the present invention is to provide a kind of solar cell, has above-mentioned organic cavity transmission layer in this battery.
The invention also discloses the application of above-mentioned organic cavity transmission layer in the preparation solar cell.
The present invention adopts metal halide that organic cavity transmission layer is carried out the P type and mixes, and namely adopts metal halides such as butter of tin, Antimony pentachloride to be doped in the hole mobile material according to a certain percentage.Behind overdoping, not only increased the quantity of charge carrier and obviously improved hole mobility and conductivity, and changed being with the position of hole mobile material and improve its photoelectric properties.This preparation method is simple, easy operating, be widely used, and the hole transmission layer of its preparation has a good application prospect in devices such as DSSC, organic solar batteries, organic inorganic hybridization solar cell.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
In the embodiments of the present invention, among the preparation method of organic cavity transmission layer, at first organic hole transferring material and organic solvent are hybridly prepared into organic hole transferring material solution; Metal halide and organic solvent are hybridly prepared into the metal halide dopant solution; Then above-mentioned organic hole transferring material solution is mixed by a certain percentage with the metal halide dopant solution and fully stir and form mixed solution.At last mixed solution is spun in the substrate, and heating, drying at a certain temperature, described hole transmission layer namely obtained.
By the doping to the organic hole transferring material, electron transition on the HUMO energy level of hole mobile material is on impurity energy level, can increase the hole concentration on the semi-conducting material ground state, thereby improve hole mobility and conductivity effectively, the electric charge transmission that reduces between semiconductor and the electrode material hinders, and improves the hole injection efficiency.Simultaneously, the minimizing of electronics on the ground state makes the material Fermi level move to the HOMO energy level, can improve photovoltage and photoelectric conversion efficiency in photovoltaic device is used.
Be described in detail below in conjunction with specific embodiment.
Embodiment 1
A certain amount of (as 90mg) spiro-OMeTAD is dissolved in the chlorobenzene (for example 0.5mL) obtains organic hole transferring material solution (solution A), a certain amount of butter of tin (for example 10g) is dissolved in the acetonitrile solution (for example 1mL) and obtains metal halide dopant solution (solution B), getting a certain amount of solution B joins among the A, ultrasonic it is fully mixed, at last mixed solution is spun in the substrate, and heating, drying at a certain temperature, namely obtain hole transmission layer.
Utilizing this hole transmission layer to be assembled into solid-state dye sensitized solar cell, is 100mWcm in intensity
-2The photoelectric properties test shows of simulated solar light source, the short-circuit current density J of this solar cell
Sc=7.52mA/cm
2, open circuit voltage V
Oc=876mV, fill factor, curve factor FF=0.47, electricity conversion η=3.10%.
The amount that is mixed into the solution B in the solution A can be according to actual needs specifically determines, for example in the present embodiment preferably value be 0.5 μ L, its doping content is 5.9% by mass fraction, also can be worth for other.
Embodiment 2
A certain amount of (as 90mg) spiro-OMeTAD is dissolved in the chlorobenzene (for example 0.5mL) obtains organic hole transferring material solution (solution A), a certain amount of butter of tin (for example 10g) is dissolved in the acetonitrile solution (for example 1mL) and obtains metal halide dopant solution (solution B), getting a certain amount of solution B joins among the A, ultrasonic it is fully mixed, obtain hole mobile material solution, at last mixed solution is spun in the substrate, and heating, drying at a certain temperature, namely obtain hole transmission layer.
Utilizing this hole transmission layer to be assembled into solid-state dye sensitized solar cell, is 100mWcm in intensity
-2The photoelectric properties test shows of simulated solar light source, the short-circuit current density J of this solar cell
Sc=7.05mA/cm
2, open circuit voltage V
Oc=858mV, fill factor, curve factor FF=0.50, electricity conversion η=3.03%.
The amount that is mixed into the solution B in the solution A can be according to actual needs specifically determines, for example in the present embodiment preferably value be 3 μ L, its doping content is 25% by mass fraction, also can be worth for other.
Embodiment 3
A certain amount of (as 30mg) P3HT is dissolved in the chlorobenzene (for example 1mL) obtains organic hole transferring material solution (solution A), a certain amount of butter of tin (for example 10g) is dissolved in the acetonitrile solution (for example 1mL) and obtains metal halide dopant solution (solution B), getting a certain amount of solution B joins among the A, ultrasonic it is fully mixed, obtain hole mobile material solution, at last mixed solution is spun in the substrate, and heating, drying at a certain temperature, hole transmission layer namely obtained.
Utilizing this hole transmission layer to be assembled into solid-state dye sensitized solar cell, is 100mWcm in intensity
-2The photoelectric properties test shows of simulated solar light source, the short-circuit current density J of this solar cell
Sc=3.46mA/cm
2, open circuit voltage V
Oc=730mV, fill factor, curve factor FF=0.63, electricity conversion η=1.59%.
The amount that is mixed into the solution B in the solution A can be according to actual needs specifically determines, for example in the present embodiment preferably value be 2 μ L, its doping content is 40% by mass fraction, also can be worth for other.
Embodiment 4
A certain amount of (as 30mg) P3HT is dissolved in the chlorobenzene (for example 1mL) obtains organic hole transferring material solution (solution A), a certain amount of butter of tin (for example 10g) is dissolved in the acetonitrile solution (for example 1mL) and obtains metal halide dopant solution (solution B), getting a certain amount of solution B joins among the A, ultrasonic it is fully mixed, obtain hole mobile material solution, at last mixed solution is spun in the substrate, and heating, drying at a certain temperature, hole transmission layer namely obtained.
Utilizing this hole transmission layer to be assembled into solid-state dye sensitized solar cell, is 100mWcm in intensity
-2The photoelectric properties test shows of simulated solar light source, the short-circuit current density J of this solar cell
Sc=3.44mA/cm
2, open circuit voltage V
Oc=740mV, fill factor, curve factor FF=0.56, electricity conversion η=1.40%.
The amount that is mixed into the solution B in the solution A can be according to actual needs specifically determines, for example in the present embodiment preferably value be 0.3 μ L, its doping content is 5.9% by mass fraction, also can be worth for other.
In the various embodiments described above, selection for the amount of organic main body hole mobile material, metal halide dopant and corresponding organic solvent, and the proportionate relationship of two kinds of solution amount of mixing is not limited to above-mentioned number range, can also select other content or ratio.General guarantee that its doping solubility is controlled by mass fraction (being the mass fraction that metal halide accounts for metal halide and organic hole transferring material sum) and get final product at 1%-50%, control better in the 5%-40% effect, in the 5.9%-25% best results.
In the various embodiments described above, bake out temperature can be chosen as 40 ℃-90 ℃.
In the various embodiments described above, base material can be TiO
2, SnO
2, ZnO, Al
2O
3, in monocrystalline silicon and the polysilicon any one.
Organic main body hole mobile material among the present invention is P3HT, spiro-OMeTAD, and poly-3-octyl group thiophene, P3OT, poly-3,4-enedioxy thiophene, at least a among PEDOT and the TPD, but be not limited to above-mentioned severally, other organic hole transferring materials all can.
Metal halide among the present invention can be at least a in butter of tin and the Antimony pentachloride, but is not limited thereto, and also can be other metal halides.
Organic solvent among the present invention can be at least a in chlorobenzene, dichloro-benzenes and the acetonitrile, but be not limited to above-mentioned severally, and other organic solvents all can.
Claims (10)
1. the preparation method of the organic cavity transmission layer of a doping metal halogenide with for the preparation of solar cell, is characterized in that, this method specifically comprises:
Machine hole mobile material and organic solvent are hybridly prepared into the step of organic hole transferring material solution;
Metal halide and organic solvent are hybridly prepared into the step of metal halide dopant solution;
Organic hole transferring material solution is mixed the step that forms mixed solution with the metal halide dopant solution; And
Mixed solution is spun in the substrate, namely obtains the step of described hole transmission layer behind the heating, drying.
2. the preparation method of the organic cavity transmission layer of a kind of doping metal halogenide according to claim 1 is characterized in that, described metal halide be doped to doping content in the organic hole transferring material by mass fraction between 1% to 50%.
3. the preparation method of the organic cavity transmission layer of a kind of doping metal halogenide according to claim 1 and 2 is characterized in that, described metal halide be doped to doping content in the organic hole transferring material by mass fraction between 5% to 40%.
4. according to the preparation method of the organic cavity transmission layer of one of claim 1-3 described a kind of doping metal halogenide, it is characterized in that, described metal halide be doped to doping content in the organic hole transferring material by mass fraction between 5.9%-25%.
5. according to the preparation method of the organic cavity transmission layer of one of claim 1-4 described a kind of doping metal halogenide, it is characterized in that, described organic hole transferring material is at least a among P3HT, spiro-OMeTAD, poly-3-octyl group thiophene, P3OT, poly-3,4-enedioxy thiophene, PEDOT and the TPD.
6. according to the preparation method of the organic cavity transmission layer of one of claim 1-5 described a kind of doping metal halogenide, it is characterized in that described metal halide is at least a in butter of tin and the Antimony pentachloride.
7. according to the preparation method of the organic cavity transmission layer of one of claim 1-6 described a kind of doping metal halogenide, it is characterized in that described organic solvent is at least a in chlorobenzene, dichloro-benzenes and the acetonitrile.
8. according to the preparation method of the organic cavity transmission layer of one of claim 1-7 described a kind of doping metal halogenide, it is characterized in that described base material is TiO
2, SnO
2, ZnO, Al
2O
3, in monocrystalline silicon and the polysilicon any one.
9. organic cavity transmission layer of utilizing the preparation of the described method of one of claim 1-8.
10. solar cell, it has organic cavity transmission layer as claimed in claim 9.
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| CN106559029A (en) * | 2016-12-06 | 2017-04-05 | 庄爱芹 | Hollow type photovoltaic glass curtain wall and preparation method thereof |
| CN108831955A (en) * | 2018-06-08 | 2018-11-16 | 苏州宝澜环保科技有限公司 | A kind of silicon solar cell and preparation method thereof |
| CN108847428A (en) * | 2018-06-08 | 2018-11-20 | 苏州宝澜环保科技有限公司 | A kind of solar battery and preparation method thereof based on silicon nanowire array |
| CN110521014A (en) * | 2017-02-20 | 2019-11-29 | 诺瓦尔德股份有限公司 | Electronic semiconductor components and the method for preparing electronic semiconductor components |
| CN112635680A (en) * | 2021-03-09 | 2021-04-09 | 江西省科学院能源研究所 | Method for deeply doping hole dopant under low concentration through temperature induction |
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| CN108831955A (en) * | 2018-06-08 | 2018-11-16 | 苏州宝澜环保科技有限公司 | A kind of silicon solar cell and preparation method thereof |
| CN108847428A (en) * | 2018-06-08 | 2018-11-20 | 苏州宝澜环保科技有限公司 | A kind of solar battery and preparation method thereof based on silicon nanowire array |
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