CN105870360A - Perovskite solar cell and preparation method thereof - Google Patents

Perovskite solar cell and preparation method thereof Download PDF

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CN105870360A
CN105870360A CN201610271359.1A CN201610271359A CN105870360A CN 105870360 A CN105870360 A CN 105870360A CN 201610271359 A CN201610271359 A CN 201610271359A CN 105870360 A CN105870360 A CN 105870360A
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conductive glass
meotad
spiro
perovskite
polycrystalline film
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CN105870360B (en
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陈冬
诸跃进
张京
黄孝坤
王鹏
徐洁
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Ningbo University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/50Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof specially adapted for light emission, e.g. organic light emitting diodes [OLED] or polymer light emitting devices [PLED]
    • H01L51/52Details of devices
    • H01L51/5203Electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L51/00Solid state devices using organic materials as the active part, or using a combination of organic materials with other materials as the active part; Processes or apparatus specially adapted for the manufacture or treatment of such devices, or of parts thereof
    • H01L51/0001Processes specially adapted for the manufacture or treatment of devices or of parts thereof
    • H01L51/0021Formation of conductors
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Abstract

The invention discloses a perovskite solar cell and a preparation method thereof. The perovskite solar cell sequentially comprises a conducting glass layer, a methylamine lead iodide polycrystalline film, a hole transport material layer and a metal electrode layer, wherein the perovskite solar cell is characterized in that the conducting glass layer is prepared by conducting glass which is subjected to interface modification; the step of interface modification comprises the following steps of: soaking the conducting glass into an organic solution of an amino silane coupling agent, standing for 5-15 minutes and then taking out the conducting glass; and drying the conducting glass at 50-100 DEG C until the conducting glass is dry. The perovskite solar cell has the advantages that interface modification is carried out on the conducting glass layer by the amino silane coupling agent; siloxy is combined with a perovskite surface which coats the conducting glass layer in a spinning manner, so that the role in improving the work function of the conducting glass is put into a play; electrons cannot be easily transmitted back after being excited from perovskite; the recombination rate of a current carrier is reduced; and the efficiency of the cell is improved.

Description

A kind of perovskite solaode and preparation method thereof
Technical field
The present invention relates to area of solar cell, particularly relate to a kind of perovskite solaode and preparation method thereof.
Background technology
Perovskite solaode is a kind of solaode based on bipolar semiconductor material, and due to its low cost, abundant raw material source, production technology is simple, and easy film forming, photo absorption performance is good, therefore suffers from the great attention of scientific research and industrial circle.Since perovskite material was used for solaode from 2009, efficiency alreadys more than 20% up till now, becoming and develop very fast low cost thin-film solar cells over nearly 3 years, the most therefore perovskite solaode is chosen as one of ten big science breakthroughs in 2013 by " Science ".
The core of perovskite solar battery structure is to have perovskite crystal formation (ABX3) organic metal halogenide light absorbent.This perovskite ABX3In structure, A is methylamino (CH3NH3), B is metallic lead atom, and X is the halogen atoms such as chlorine, bromine, iodine.At present in the Ca-Ti ore type solaode of classical architecture, modal perovskite organic metal halogenide light absorbent is lead iodide methylamine (CH3NH3PbI3), its band gap is about 1.5 eV, and extinction coefficient are high, and the thin film of hundreds of nano thickness just can fully absorb the sunlight of below 800 nanometers.And in preparation process, generally will be containing PbI2And CH3NH3The solution of I, can obtain the uniform thin film of this material at normal temperatures by spin coating.Above-mentioned characteristic makes the battery of this perovskite structure can realize visible ray and the absorption of part near infrared light, and this is also so that Ca-Ti ore type solaode is capable of high efficiency major reason.
Perovskite solaode has various structures at present: see battery, the plane battery without poriferous titanium dioxide, Jie's sight battery of the superstructure containing porous insulation oxide (such as aluminium sesquioxide, zirconium oxide) etc. containing being situated between of poriferous titanium dioxide.Although the various structures of battery, preparation method is the most more, but interface is inevitably present in various battery.And the transmission that electronics is at multiple interfaces can inevitably affect the opto-electronic conversion performance of perovskite battery.
Although the electronic transmission performance of perovskite self is the best, but in interface, the efficiency of transmission of electronics often relies on perovskite coverage condition on adjacent film layers interface.But the perovskite coverage condition prepared by solwution method is the most undesirable, causes the passback of interface inside battery electronics.The passback of this electronics can cause the open-circuit voltage of battery under illumination and fill factor, curve factor to reduce, and electronics can not effectively spread out of, and has had a strong impact on the photoelectric transformation efficiency of battery.
Therefore, prior art there is the problem that perovskite solar cell interface electronics is compound serious, constrains the photoelectric transformation efficiency of battery.
Summary of the invention
The technical problem to be solved is to provide one can reduce cell interface electronics recombination rate, improves perovskite solaode of cell photoelectric conversion efficiency and preparation method thereof.
The present invention solves the technical scheme that above-mentioned technical problem used: a kind of perovskite solaode, include conductive glass layer, methylamine lead iodine polycrystalline film, hole transport material and metal electrode layer successively, described conductive glass layer is made up of the electro-conductive glass after modifying interface, described modifying interface refers to be immersed in the organic solution of amino silicane coupling agent electro-conductive glass, take out after standing 5 ~ 15 minutes, then dry at 50 ~ 100 DEG C to being dried.Wherein, drying time is about 5 ~ 20 minutes, as long as and carrying out silane coupled silane coupler and be used equally to the present invention.
In some embodiments, described amino silicane coupling agent is 3-aminopropyl triethoxysilane.Thus, there is the effect preferably improving battery efficiency.
In some embodiments, electron transfer layer is not comprised.Thus, it is possible to improve battery efficiency while saving production cost, it is more beneficial for industrialization on a large scale and produces.
In some embodiments, described hole transport material is prepared by spiro-MeOTAD.Thus, there is preferably photoelectric conversion result.
In some embodiments, described methylamine lead iodine polycrystalline film thickness is 200 nanometer ~ 1.5 micron, and described hole transport material thickness is 50 ~ 500 nanometers, and described metal electrode layer thickness is 50 ~ 200 nanometers.Thus, there is preferably photoelectric conversion result.
The preparation method of a kind of above-mentioned perovskite solaode, comprises the following steps:
1. electro-conductive glass is carried out modifying interface, particularly as follows: electro-conductive glass is immersed in the organic solution of amino silicane coupling agent, take out after standing 5 ~ 15 minutes, then dry at 50 ~ 100 DEG C to being dried, using this electro-conductive glass as modified conductive glass layer;
2. iodine methylamine and lead chloride being dissolved in DMF with mol ratio 5:1 ~ 1:1, use sol evenning machine by above-mentioned solution deposition on modified conductive glass layer, control temperature 70 ~ 150 DEG C, crystallization obtains methylamine lead iodine polycrystalline film;
3. the organic solution of hole mobile material is spin-coated on equably in methylamine lead iodine polycrystalline film;
4. evaporation coating method is used, evaporation metal electrode layer on above-mentioned multilayer film.
The organic solution of described amino silicane coupling agent is the ethanol solution of amino silicane coupling agent, and concentration is 0.01 ~ 0.05M.
Stating hole mobile material is spiro-MeOTAD, step is 3. particularly as follows: be dissolved in the spiro-MeOTAD that concentration is 0.5 ~ 1.5M in chlorobenzene, add tetrabutyl pyridine and double trifluoromethanesulfonimide lithiums of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, then the solution of above-mentioned spiro-MeOTAD is spin-coated in methylamine lead iodine polycrystalline film equably.
Compared with prior art, it is an advantage of the current invention that: employ amino silicane coupling agent and conductive glass layer is carried out modifying interface, silane epoxide combines with the perovskite surface being spin-coated on conductive glass layer, serve the effect improving electro-conductive glass work function, electronics can be made to be difficult to return after perovskite excites, thus reduce the recombination rate of carrier, improve battery efficiency.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but not as a limitation of the invention.
Embodiment 1: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.01M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.01M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 10 minutes, then 100 DEG C of bakings are evaporated to solvent for 10 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 3.89%(short-circuit current density 12.11mA/cm2, open-circuit voltage 0.788V, fill factor, curve factor 0.406), than the most modified solar battery efficiency (3.52%, short-circuit current density 12.75mA/cm2, open-circuit voltage 0.708V, fill factor, curve factor 0.384) improve about 11%.The reason improved is mainly the conductive glass layer of battery and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve battery fill factor, curve factor and open-circuit voltage, therefore the photoelectric transformation efficiency of perovskite solaode improves.
Embodiment 2: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0125M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0125M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 10 minutes, then 100 DEG C of bakings are evaporated to solvent for 10 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 4.01%(short-circuit current density 11.95mA/cm2, open-circuit voltage 0.791V, fill factor, curve factor 0.417), than the most modified solar battery efficiency (3.52%, short-circuit current density 12.75mA/cm2, open-circuit voltage 0.708V, fill factor, curve factor 0.384) improve about 15%.The reason improved is mainly the conductive glass layer of battery and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve battery fill factor, curve factor and open-circuit voltage, therefore the photoelectric transformation efficiency of perovskite solaode improves.
Embodiment 3: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.025M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.025M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 10 minutes, then 100 DEG C of bakings are evaporated to solvent for 10 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 5.37%(short-circuit current density 14.72mA/cm2, open-circuit voltage 0.901V, fill factor, curve factor 0.398), improve about 40% than undressed solar battery efficiency (3.52%).The reason improved is mainly battery conductive glassy layer and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve short circuit current and open-circuit voltage, therefore the photoelectric transformation efficiency of perovskite solaode improves.
Embodiment 4: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0375M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 10 minutes, then 100 DEG C of bakings are evaporated to solvent for 10 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 7.34%(short-circuit current density 20.51mA/cm2, open-circuit voltage 0.860V, fill factor, curve factor 0.409), it is doubled many than undressed solar battery efficiency (3.52%).The reason improved is mainly battery conductive glassy layer and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve short circuit current, open-circuit voltage and battery fill factor, curve factor, therefore the photoelectric transformation efficiency of perovskite solaode improves, and the amino silicane coupling agent concentration of the present embodiment is more excellent compared with the concentration of above-described embodiment.
Embodiment 5: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.05M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.05M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 10 minutes, then 100 DEG C of bakings are evaporated to solvent for 10 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 4.23%(short-circuit current density 13.22mA/cm2, open-circuit voltage 0.842V, fill factor, curve factor 0.374), improve 20% than undressed solar battery efficiency (3.52%).The reason improved is mainly battery conductive glassy layer and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve open-circuit voltage and battery fill factor, curve factor, therefore the photoelectric transformation efficiency of perovskite solaode improves.But the modification concentration of amino silicane coupling agent is relatively big in the present embodiment, can affect the transmission of inside battery normal electrical, therefore, compare the first two embodiment, the photoelectric transformation efficiency increase rate of perovskite solaode decreases.
Embodiment 6: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0375M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 5 minutes, then 50 DEG C of bakings are evaporated to solvent for 20 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 5.06%.
Embodiment 7: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0375M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 8 minutes, then 80 DEG C of bakings are evaporated to solvent for 15 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 6.89%.
Embodiment 8: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0375M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 12 minutes, then 100 DEG C of bakings are evaporated to solvent for 5 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 6.72%.
Embodiment 9: preparation concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution, carries out modifying interface to conductive glass layer.
First 3-aminopropyl triethoxysilane being dissolved in ethanol, concentration is 0.0375M.Conductive glass layer is soaked in above-mentioned solution, takes out after standing 15 minutes, then 100 DEG C of bakings are evaporated to solvent for 8 minutes, obtain the conductive glass layer of modification.
Again by CH3NH3I and PbCl2It is dissolved in DMF (DMF) with mol ratio 3:1, uses sol evenning machine by above-mentioned solution deposition on the conductive glass layer of above-mentioned modification.Toasted 1 hour at 90 DEG C by precise control of temperature so that crystallization becomes methylamine lead iodine polycrystalline film.
In the chlorobenzene solution (concentration is 0.6M) of hole mobile material spiro-MeOTAD, add tetrabutyl pyridine (tBP) and double trifluoromethanesulfonimide lithiums (Li-TFSI) of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, the solution of above-mentioned spiro-MeOTAD is spin-coated on equably in methylamine lead iodine polycrystalline film.
The method using evaporation, evaporation metal electrode layer on above-mentioned multilayer film, is silver electrode layer in the present embodiment.
In the present embodiment, methylamine lead iodine polycrystalline film thickness is 600 nanometers,Hole transport material thickness is 300 nanometers,Evaporation silver electrode layer thickness is 90 nanometers.
At room temperature environment, using xenon lamp simulated solar irradiation, light intensity is 95.6mW/cm2Under the conditions of (solar simulator model: Newport91192A), (effective illuminating area is 0.07cm to record the perovskite solaode of modified2) photoelectric transformation efficiency be 7.05%.
Perovskite solaode has various structures, which includes electron transfer layer and the perovskite solaode without electron transfer layer.Owing to the preparation of electron transfer layer typically requires hot environment, and produce hot environment and need to consume substantial amounts of energy, so that production cost increases, and it is unfavorable for realizing the large-scale production of perovskite solaode, therefore embodiments of the invention are the preparation method without electron transfer layer perovskite solaode.
Wherein, it is the prior art known to person of ordinary skill in the field that the condition in perovskite solaode preparation process selects, and has therefore only selected more common parameter to test in embodiments of the invention, should not be a limitation of the present invention.Except special instruction, experiment reagent involved in the present invention all can be by being either commercially available.
In sum, present invention concentration is the 3-aminopropyl triethoxysilane (C of 0.0375M9H23NO3Si) ethanol solution carries out modifying interface to conductive glass layer, and the photoelectric transformation efficiency of obtained perovskite solaode is more excellent is 7.34%, and than under the same terms, undressed solar battery efficiency (3.52%) is doubled many.The reason improved is mainly battery conductive glassy layer and modifies through amino silicane coupling agent, the compound of electronics is decreased in the interface adjacent with methylamine lead iodine polycrystalline film, thus improve short circuit current, open-circuit voltage and battery fill factor, curve factor, therefore the photoelectric transformation efficiency of perovskite solaode improves.

Claims (8)

1. a perovskite solaode, include conductive glass layer, methylamine lead iodine polycrystalline film, hole transport material and metal electrode layer successively, it is characterized in that, described conductive glass layer is made up of the electro-conductive glass after modifying interface, described modifying interface refers to be immersed in the organic solution of amino silicane coupling agent electro-conductive glass, take out after standing 5 ~ 15 minutes, then dry at 50 ~ 100 DEG C to being dried.
2. a kind of perovskite solaode as claimed in claim 1, it is characterised in that described amino silicane coupling agent is 3-aminopropyl triethoxysilane.
3. a kind of perovskite solaode as claimed in claim 1, it is characterised in that do not comprise electron transfer layer.
4. a kind of perovskite solaode as claimed in claim 1, it is characterised in that described hole transport material is prepared by spiro-MeOTAD.
5. a kind of perovskite solaode as described in any one of claim 1-4, it is characterized in that, described methylamine lead iodine polycrystalline film thickness is 200 nanometer ~ 1.5 micron, and described hole transport material thickness is 50 ~ 500 nanometers, and described metal electrode layer thickness is 50 ~ 200 nanometers.
6. the preparation method of the perovskite solaode described in an any one of claim 1-4, it is characterised in that comprise the following steps:
1. electro-conductive glass is carried out modifying interface, particularly as follows: electro-conductive glass is immersed in the organic solution of amino silicane coupling agent, take out after standing 5 ~ 15 minutes, then dry at 50 ~ 100 DEG C to being dried, using this electro-conductive glass as modified conductive glass layer;
2. iodine methylamine and lead chloride being dissolved in DMF with mol ratio 5:1 ~ 1:1, use sol evenning machine by above-mentioned solution deposition on modified conductive glass layer, control temperature 70 ~ 150 DEG C, crystallization obtains methylamine lead iodine polycrystalline film;
3. the organic solution of hole mobile material is spin-coated on equably in methylamine lead iodine polycrystalline film;
4. evaporation coating method is used, evaporation metal electrode layer on above-mentioned multilayer film.
7. the preparation method of perovskite solaode as claimed in claim 6, it is characterised in that the organic solution of described amino silicane coupling agent is the ethanol solution of amino silicane coupling agent, and concentration is 0.01 ~ 0.05M.
8. the preparation method of perovskite solaode as claimed in claim 6, it is characterized in that, described hole mobile material is spiro-MeOTAD, step is 3. particularly as follows: be dissolved in the spiro-MeOTAD that concentration is 0.5 ~ 1.5M in chlorobenzene, add tetrabutyl pyridine and double trifluoromethanesulfonimide lithiums of 30%spiro-MeOTAD molal quantity of 80%spiro-MeOTAD molal quantity, then the solution of above-mentioned spiro-MeOTAD is spin-coated in methylamine lead iodine polycrystalline film equably.
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