CN108649125B - A method of improving perovskite material humidity stability - Google Patents

A method of improving perovskite material humidity stability Download PDF

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CN108649125B
CN108649125B CN201810563019.5A CN201810563019A CN108649125B CN 108649125 B CN108649125 B CN 108649125B CN 201810563019 A CN201810563019 A CN 201810563019A CN 108649125 B CN108649125 B CN 108649125B
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perovskite material
perovskite
humidity stability
hydrophobic chain
improving
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CN108649125A (en
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叶谦
章琎
郭鹏飞
王洪强
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Northwestern Polytechnical University
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    • H—ELECTRICITY
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • Y02E10/549—Organic PV cells

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Abstract

The invention discloses a kind of methods for improving perovskite humidity stability, that is, by introducing fluorine carbon hydrophobic chain molecule RNH2The preparation and perovskite material and modified two steps of fluorine carbon hydrophobic chain molecular mixing to improve the humidity stability of perovskite material, including perovskite material are surface modified to perovskite material.Perovskite material is modified using hydrophobic chain molecule in the present invention, its surface defect that amino can make in conjunction with Perovskite Phase is reduced and carrier lifetime increases, alkyl chain and C-F functional group can improve the hydrophobicity of material surface, finally it is obviously improved the photoelectric properties of perovskite material and moisture stable performance, the service life of perovskite-based photoelectric device is extended simultaneously, so that perovskite material has fine development prospect in the practical application of photoelectric field.

Description

A method of improving perovskite material humidity stability
Technical field
The present invention relates to perovskite-based technical field of photoelectric material preparation, specially a kind of raising perovskite material humidity is steady Qualitative method.
Background technique
In recent years, with CH3NH3PbI3It is rapidly developed, has become for the hybrid inorganic-organic perovskite material of representative For most potential photovoltaic material.Compared with other semiconductor materials, perovskite material has excellent photoelectric property, has The excellent properties such as absorptivity height, longer, the bipolarity carrier transport of exciton diffusion length, and preparation process is simple, these are excellent Point makes perovskite be not only ideal solar cell material, leads in other photoelectricity such as light emitting diode, laser and optical detector Domain is also widely used.
Photoelectric device has general two big important technology indexs, and photoelectric conversion efficiency and device including device use the longevity Life.In recent years, having obtained extensive research, calcium titanium in relation to the efficient solar battery of perovskite and sensitive optical detector The excellent photoelectric properties of pit wood material are constantly confirmed.But the stability problem of perovskite material has become restriction perovskite The bottleneck of photoelectric device development, especially humidity stability, moisture can be such that it gradually decomposes, lead to the decline of photoelectric property.
Summary of the invention
The present invention is directed to perovskite labile problem in air, provides a kind of raising perovskite material humidity stability Method, i.e., perovskite material is surface modified by fluorine carbon hydrophobic chain molecule, obtain high efficiency and humidity stability it is excellent Different perovskite material.By fluorine carbon hydrophobic chain molecule to perovskite material surface modification while improving stability test, It can also achieve the purpose that passivated surface defect by the introducing of the active function groups of molecular end, to effectively promote perovskite The photoelectric conversion performance of material,
To achieve the above object, the technical solution adopted by the present invention are as follows:
A method of perovskite material humidity stability being improved, by introducing fluorine carbon hydrophobic chain RNH2Molecule is to perovskite Material is surface modified to improve the humidity stability of perovskite material, wherein fluorine carbon hydrophobic chain RNH2Molecule is CnF2n+ 1NH2, CnF2n+1CH2NH2, CnF2n+1CH2CH2NH2And CnF2n+1CH2CH2CH2NH2One of or it is a variety of, wherein n be >=6, including Following steps:
Step 1 weighs lead halide and halogenation methylamine respectively and prepares solution using solvent dissolution, by prepared lead halide Solution is slowly added drop-wise in halogenation methylamine solution at room temperature, and 30min~2h is stirred under atmosphere of inert gases, obtains perovskite Material；
A certain proportion of Hydrophobic small molecules RNH is added into the perovskite material that step 1 obtains for step 22, after stirring To the perovskite material of modification.
Preferably, the molar ratio of lead halide and halogenation methylamine is 1:1~1.1 in step 1.
Preferably, the solvent in step 1 for dissolving lead halide is formamide, acetamide, N-METHYLFORMAMIDE, N, N- bis- One of methylformamide, n,N-dimethylacetamide and dimethyl sulfoxide are a variety of, for dissolving the solvent of halogenation methylamine For isopropanol, the inert atmosphere is nitrogen or argon gas.
Preferably, perovskite material includes the perovskite quantum dot of zero dimension, one-dimensional perovskite Nano/micron in step 1 The perovskite particle of line, two-dimensional perovskite nanometer sheet and three-dimensional.
Preferably, fluorine carbon hydrophobic chain molecule RNH in step 22Mass ratio with perovskite material is 0.05~0.5:1, instead Answering temperature is 0 DEG C~60 DEG C, and the reaction time is 30min~4h.
Compared with prior art, beneficial effects of the present invention are as follows:
1, preparation method of the invention is simple, and mild condition is low in cost, while preparation process controllability is high.
2, perovskite material surface defect prepared by the present invention reduces, and carrier lifetime increases, which is answered When for optical detector, responsiveness rises to 1.27A/W from 0.52A/W, and when being applied to solar battery, efficiency increases from 11% To 15%.
3, the humidity stability of perovskite material of the invention has apparent improvement, is 55% ± 5% in relative humidity Under conditions of, the detector and solar battery prepared using the perovskite material in the present invention is several without encapsulation placement 30 days It does not decompose, photoelectric properties still keep initial 80% or more.
Specific embodiment
The present invention is described in detail below in conjunction with specific embodiment, so that those skilled in the art can be more The good understanding present invention can be simultaneously practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
According to the score also known as amount 461.01mg lead iodide (PbI of the amount of the substance of 1:12) and 158.97mg iodate methylamine (CH3NH3I), by PbI2It is dissolved in stirring 2h in the N,N-dimethylformamide (DMF) of 1mL and obtains the N of lead iodide, N- dimethyl Formamide solution, by CH3NH3I is dissolved in stirring 2h in the aqueous isopropanol of 20mL and obtains the aqueous isopropanol of iodate methylamine, so The n,N-Dimethylformamide solution of lead iodide is slowly dropped in the aqueous isopropanol of iodate methylamine under argon atmosphere afterwards, Continue stirring 20min and obtain flaxen suspension, the perfluoro capryl second of the 0.05mol% of 10 μ L is finally added into suspension Amine, stirs 30min, and the perovskite micro wire modified is denoted as 1#.
Embodiment 2
According to the score also known as amount 461.01mg lead iodide (PbI of the amount of the substance of 1:12) and 158.97mg iodate methylamine (CH3NH3I), by PbI2It is dissolved in stirring 2h in the N,N-dimethylformamide (DMF) of 1mL and obtains the N of lead iodide, N- dimethyl Formamide solution, by CH3NH3I is dissolved in stirring 2h in the aqueous isopropanol of 20mL and obtains the aqueous isopropanol of iodate methylamine, so The n,N-Dimethylformamide solution of lead iodide is slowly dropped in the aqueous isopropanol of iodate methylamine under argon atmosphere afterwards, Continue stirring 20min and obtain flaxen suspension, the perfluoro capryl of the 0.05mol% of 10 μ L is finally added into suspension Amine, stirs 30min, and the perovskite micro wire modified is denoted as 2#.
Embodiment 3
According to the score also known as amount 461.01mg lead iodide (PbI of the amount of the substance of 1:12) and 158.97mg iodate methylamine (CH3NH3I), the n,N-Dimethylformamide (DMF) of 800 μ L and the diformazan of 200 μ L are then weighed respectively according to the volume ratio of 4:1 Base sulfoxide is simultaneously mixed to get mixed solvent, then by PbI2And CH3NH3I is added in the mixed solvent and stirs 3h at 50 DEG C, Obtain perovskite precursor solution；Compound concentration is that the chlorobenzene solution of the perfluoro capryl ethamine of 0.2mg/mL is stand-by.
The perovskite micro wire being prepared in embodiment 1 and embodiment 2 is further assembled optical detector by us, is gone forward side by side The test of row photoelectric properties.1# suspension and 2# suspension are made calcium titanium respectively with revolving speed spin coating 10 times of 2000rpm by us first Substrate of glass is completely covered in mine micro wire, and 30min is then heated at 100 DEG C, then 300nm Au electricity is deposited under condition of high vacuum degree Pole obtains 1# optical detector and 2# optical detector.
We carry out photoelectric properties test to 1# optical detector and 2# optical detector, and the responsiveness of 1# optical detector is 1.35A/W, and under conditions of relative humidity is 55% ± 5%, no encapsulation places 30 days photoelectric currents and still keeps initial 88%, Without being only original 25% under perovskite optical detector the same terms of modification.The responsiveness of 2# optical detector is 1.27A/ W, and under conditions of relative humidity is 55% ± 5%, no encapsulation places 30 days photoelectric currents and still keeps initial 85%, without The responsiveness of the perovskite material of modification is 0.52A/W, and photoelectric current is only original 30% after placing 30 days under the same terms.
The perovskite precursor solution that we obtain embodiment 3 is applied in solar battery, first in clean FTO On with spin-coating method prepare TiO2Layer, in 500 DEG C of annealing 1h.Then precursor solution embodiment 3 obtained in glove box with The revolving speed of 2000rpm is spin-coated on TiO2On layer, the concentration that 200 μ L are added dropwise during spin coating is the perfluoro capryl of 0.2mg/mL The chlorobenzene of amine obtains perovskite light-absorption layer as anti-solvent, in 100 DEG C of heating 60min, finally again with the revolving speed spin coating of 5000rpm The Au electrode of one layer of 100nm thickness is deposited as hole transmission layer in the Spiro of 72mg/mL, and solar battery can be obtained.
We have carried out performance test to obtained solar battery, and the efficiency of the solar battery is 15%, opposite Under conditions of humidity is 55% ± 5%, no encapsulation places 30 days photoelectric currents and still keeps initial 80%, without the calcium titanium of modification The corresponding efficiency of pit wood material is 11%, and photoelectric current is only original 25% after placing 30 days under the same terms.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the principle of the present invention, it can also make several improvements and retouch, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims (5)

1. a kind of method for improving perovskite material humidity stability, which is characterized in that by introducing fluorine carbon hydrophobic chain RNH2Molecule Perovskite material is surface modified to improve the humidity stability of perovskite material, the fluorine carbon hydrophobic chain RNH2Molecule is CnF2n+1NH2, CnF2n+1CH2NH2, CnF2n+1CH2CH2NH2And CnF2n+1CH2CH2CH2NH2One of or it is a variety of, wherein n be >= 6, comprising the following steps:
Step 1 weighs lead halide and halogenation methylamine respectively and prepares solution using solvent dissolution, by prepared halogenation lead solution It is slowly dropped in halogenation methylamine solution at room temperature, 30min~2h is stirred under atmosphere of inert gases, obtains perovskite material Material；
A certain proportion of fluorine carbon hydrophobic chain RNH is added into the perovskite material that step 1 obtains for step 22Molecule obtains after stirring The perovskite material of modification.
2. a kind of method for improving perovskite material humidity stability according to claim 1, which is characterized in that step 1 The molar ratio of middle lead halide and halogenation methylamine is 1:1~1.1.
3. a kind of method for improving perovskite material humidity stability according to claim 1, which is characterized in that step 1 In for dissolve lead halide solvent be formamide, acetamide, N-METHYLFORMAMIDE, N,N-dimethylformamide, N, N- diformazan One of yl acetamide and dimethyl sulfoxide are a variety of, and the solvent for dissolving halogenation methylamine is isopropanol, the indifferent gas Body atmosphere is nitrogen or argon gas.
4. a kind of method for improving perovskite material humidity stability according to claim 1, which is characterized in that step 1 The perovskite material includes that the perovskite quantum dot, one-dimensional perovskite Nano/micron line, two-dimensional perovskite of zero dimension are received Rice piece and three-dimensional perovskite particle.
5. a kind of method for improving perovskite material humidity stability according to claim 1, which is characterized in that step 2 The fluorine carbon hydrophobic chain RNH2The mass ratio of molecule and perovskite material is 0.05~0.5:1, and reaction temperature is 0 DEG C~60 DEG C, the reaction time is 30min~4h.
CN201810563019.5A 2018-06-04 2018-06-04 A method of improving perovskite material humidity stability Expired - Fee Related CN108649125B (en)

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CN110867519A (en) * 2019-11-26 2020-03-06 吉林大学 Light emitting diode and preparation method thereof
CN110887811B (en) * 2019-12-03 2023-01-13 南方科技大学 Perovskite-based composite material for laser humidity sensor, and preparation method and application thereof
CN111816772B (en) * 2020-06-22 2024-03-08 隆基绿能科技股份有限公司 Perovskite solar cell, production method thereof and perovskite cell assembly
CN111933802B (en) * 2020-08-18 2024-04-19 昆山协鑫光电材料有限公司 Application of ionic liquid in preparation of perovskite photosensitive layer and perovskite solar cell
CN113340948A (en) * 2021-06-09 2021-09-03 重庆大学 Preparation method of high-response humidity sensor based on halogenated perovskite microcrystal and product thereof

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