CN104752065A - Preparing method of methyl amino bismuth iodide photovoltaic film - Google Patents

Preparing method of methyl amino bismuth iodide photovoltaic film Download PDF

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Publication number
CN104752065A
CN104752065A CN201510173613.XA CN201510173613A CN104752065A CN 104752065 A CN104752065 A CN 104752065A CN 201510173613 A CN201510173613 A CN 201510173613A CN 104752065 A CN104752065 A CN 104752065A
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bismuth iodide
temperature
methylamine
methylamino
solution
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CN201510173613.XA
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徐金宝
王贺勇
王磊
边亮
任卫
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a preparing method of methyl amino bismuth iodide photovoltaic film. The method includes: mixing methylamine and hydroiodic acid, allowing reaction at low temperature, performing evaporating and drying to obtain methylamine iodine powder, dissolving the methylamine iodine powder and bismuth iodide powder in dimethyl formamide or V-butyrolactone solution, performing heating and stirring to allow dissolution, subjecting a substrate to spin-coating, and performing heating and crystallizing at set temperature so as to obtain the methyl amino bismuth iodide film. The method has the advantages of simplicity in process, low cost, good environment friendliness, ease of large-scale production and the like. The methyl amino bismuth iodide prepared by the method has bandgaps in a visible light area, I-V curve testing of a solar cell device prepared shows that photoelectric conversion performance is good, and the method is applicable to the field of solar cell photovoltaics.

Description

A kind of preparation method of methylamino bismuth iodide photovoltaic film
Technical field
The invention belongs to field of material preparation, relate to a kind of preparation method of methylamino bismuth iodide photovoltaic film, the methylamino bismuth iodide photovoltaic film obtained by the method for the invention shows good photovoltaic property.
Background technology
Energy problem is all global problem all the time, and along with the minimizing of oil coal resources, energy crisis displays again.The alleviation energy problem that is applied as of photovoltaic technology brings hope.
After fuel sensitization solar battery, organic inorganic hybridization perovskite solar cell becomes new study hotspot, and presents the development of advancing by leaps and bounds in nearly photoelectric efficiency in two years.Organic inorganic hybridization perovskite material basic structure formula is ABX 3, wherein A position aliphat or aromatic series, B position is divalent metal, and X position is halide ion.In present report, A position great majority adopt Cs +, CN 3nH 3 +, NH 2cHNH 2 +, B position adopts has bivalent metal ion, such as Pb 2+and Sn 2+, X position adopts single halogen or mixing halogen.T. organic inorganic hybridization leaded halogen was applied in perovskite fuel sensitization solar battery in 2006 by Miyaska first, and efficiency reaches 2.19%.At present, CH 3nH 3pbX 3(X=I, Cl, Br) perovskite solar cell adopts different structures and preparation technology to prepare the battery of efficiency more than 20%.But lead element belongs to toxic element, excessive use has very large harm to human body and environment.From market scaleization application, need badly and prepare environmentally friendly lead free solar cell.
Sol-gel technique has been widely used in the various function film of preparation, as ferroelectric and dielectric film, and photocatalysis membrana, non-linear optical film and high temperature superconducting film etc.The method main technological features is: (1) equipment is simple; (2) post-processing temperature is low; For masking in the poor substrate of thermal stability or the meaning thin film deposition of poor heat stability in substrate with particular importance; (3) to the shape of substrate and size requirements lower; (4) easily with effectively control thin film composition and microstructure.The present invention adopts sol-gal process to prepare methylamino bismuth iodide photovoltaic film.
Summary of the invention
The object of the invention is, a kind of preparation method of methylamino bismuth iodide photovoltaic film is provided, the method utilizes methylamine and hydroiodic acid mixing, react in low temperature environment, then evaporation drying obtains methylamine iodine powder, then is dissolved in dimethyl formamide or gamma-butyrolacton solution by methylamine iodine powder and bismuth iodide powder, after heating stirring and dissolving, by being spin-coated on substrate, and at the temperature of setting heating crystallization, form methylamino bismuth iodide film.It is simple that the method for the invention has technique, and cost is low, environmental friendliness, is easy to the advantages such as large-scale production.The methylamino bismuth iodide band gap obtained by the method for the invention, in visible region, surveys I-V curve after being prepared into solar cell device, have good opto-electronic conversion performance, can be used for solar cell photovoltaic field.
The preparation method of a kind of methylamino bismuth iodide photovoltaic film of the present invention, the method for raw material, uses sol-gal process with methylamine, hydroiodic acid, bismuth iodide, by controlling solution concentration and heating time, obtain methylamino bismuth iodide film, concrete operations follow these steps to carry out:
A, be that 1:1-1.5 mix in molar ratio by methylamine and hydroiodic acid, react in DEG C environment of low temperature-10 DEG C-10, time 1-2h, then heat up 50 DEG C-70 DEG C evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 30 DEG C-80 DEG C, then cool to-30-0 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, the finally DEG C heating evaporation in temperature 50 C-70, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a to be dissolved in organic solvent be that in dimethyl formamide or gamma-butyrolacton, stirring at room temperature, is configured to the methylamine iodine solution that concentration is 0.3-1.5mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 1.5-3:1, is configured to the solution of concentration 0.1-0.5mol/L, adds thermal agitation, and solution is clarified;
D, get step c gained solution and drop on tin oxide transparent conductive glass, tin indium oxide transparent conductive glass or the Si sheet that substrate is doped with fluorine, use the spin coating 10-20 seconds under the rotating speed of 2000-4000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 100-150 DEG C, is heating 5-10min, namely obtain methylamino bismuth iodide film.
In step a, reaction temperature is 0 DEG C.
In step a, methylamine iodine Precipitation Temperature is-10 DEG C--20 DEG C.
Evaporating temperature 60 DEG C in step a.
The preparation method of a kind of methylamino bismuth iodide photovoltaic film of the present invention, the methylamino bismuth iodide film prepared by the method is unleaded organic inorganic hybridization photovoltaic film material in, band gap, in visible region, has good absorbing properties, can apply and photovoltaic field.
Methylamino bismuth iodide membrane structure prepared by the method for the invention has size uniform, the feature that thickness is controlled, can photoelectric device instructions for use be met.
Accompanying drawing illustrates:
Fig. 1 is the photoelectric efficiency figure that the sample preparation of the embodiment of the present invention 1 gained becomes device to record;
Fig. 2 is that the surface diffuse reflectance of the embodiment of the present invention 1 gained sample absorbs spectrogram;
Fig. 3 is X-ray diffraction (XRD) spectrum of the embodiment of the present invention 1 gained sample, wherein-☆-and be product peak,---be FTO substrate peak;
Fig. 4 is that the surface diffuse reflectance of the embodiment of the present invention 2 gained sample absorbs spectrogram;
Fig. 5 is that the surface diffuse reflectance of the embodiment of the present invention 3 gained sample absorbs spectrogram;
Fig. 6 is that the surface diffuse reflectance of the embodiment of the present invention 4 gained sample absorbs spectrogram.
Embodiment:
Embodiment 1
1:1.2 mixing pressed by a, methylamine and hydroiodic acid, reacts, time 2h in low temperature-10 DEG C of environment, then heat up 50 DEG C of evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 30 DEG C, then cool to-30 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, last at temperature 50 C heating evaporation, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a is dissolved in organic solvent is in dimethyl formamide, and stirring at room temperature, is configured to the methylamine iodine solution that concentration is 0.3mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 3:1, is configured to the solution of concentration 0.1mol/L, adds thermal agitation, and solution is clarified;
D, get step c gained solution and drop on the tin oxide transparent conductive glass that substrate is doped with fluorine, use the spin coating 10 seconds under the rotating speed of 2000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 100 DEG C, is heating 5min, namely obtain methylamino bismuth iodide film.
Embodiment 2
A, methylamine and hydroiodic acid are 1:1.5 mixing in molar ratio, react, time 1h in low temperature-5 DEG C of environment, then heat up 60 DEG C of evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 50 C, then cool to-10 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, last at temperature 60 C heating evaporation, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a is dissolved in organic solvent is in gamma-butyrolacton, and stirring at room temperature, is configured to the methylamine iodine solution that concentration is 0.8mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 2:1, is configured to the solution of concentration 0.4mol/L, adds thermal agitation, and solution is clarified;
D, getting step c gained solution, to drop in substrate be on tin indium oxide transparent conductive glass, uses the spin coating 12 seconds under the rotating speed of 3000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 120 DEG C, is heating 8min, namely obtain methylamino bismuth iodide film.
Embodiment 3
A, methylamine and hydroiodic acid are 1:1 mixing in molar ratio, react, time 2h in low temperature 0 DEG C of environment, then heat up 70 DEG C of evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 65 DEG C, then cool to-10 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, last at temperature 70 C heating evaporation, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a is dissolved in organic solvent is in dimethyl formamide, and stirring at room temperature, is configured to the methylamine iodine solution that concentration is 1.0mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 2.5:1, is configured to the solution of concentration 0.4mol/L, adds thermal agitation, and solution is clarified;
D, getting step c gained solution, to drop in substrate be on Si sheet, uses the spin coating 20 seconds under the rotating speed of 4000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 150 DEG C, is heating 10min, namely obtain methylamino bismuth iodide film.
Embodiment 4
A, methylamine and hydroiodic acid are 1:1.1 mixing in molar ratio, react, time 2h in low temperature 10 DEG C of environment, then heat up 60 DEG C of evaporations, obtains methylamine iodine powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 45 C, then cool to 0 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, last at temperature 60 C heating evaporation, drying, obtains powder, collects stand-by;
B, be dissolved in organic solvent gamma-butyrolacton by the methylamine iodine powder obtained in step a, stirring at room temperature, is configured to the methylamine iodine solution that concentration is 1.5mol/L, is placed in beaker;
C, in molar ratio bismuth iodide to be added in the methylamine iodine solution of gained in step b, be configured to the solution of concentration 0.5mol/L, add thermal agitation, solution is clarified;
D, get step c gained solution and drop on the tin oxide transparent conductive glass that substrate is doped with fluorine, use the spin coating 10 seconds under the rotating speed of 2000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 110 DEG C, is heating 8min, namely obtain methylamino bismuth iodide film.
Embodiment 5
A, methylamine and hydroiodic acid are 1:1 mixing in molar ratio, react, time 2h in low temperature 0 DEG C of environment, then heat up 60 DEG C of evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 80 DEG C, then cool to-20 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, last at temperature 70 C heating evaporation, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a is dissolved in organic solvent is in dimethyl formamide, and stirring at room temperature, is configured to the methylamine iodine solution that concentration is 1.2mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 2.4:1, is configured to the solution of concentration 0.5mol/L, adds thermal agitation, and solution is clarified;
D, getting step c gained solution, to drop in substrate be on tin indium oxide transparent conductive glass, uses the spin coating 15 seconds under the rotating speed of 3000r/min of spin coating instrument;
E, steps d gained sample is being placed on temperature control platform, at temperature 150 DEG C, is heating 10min, namely obtain methylamino bismuth iodide film.
Embodiment 6
The methylamino bismuth iodide film preparation obtained by the method for the invention becomes solar cell, uses xenon lamp light source simulated solar irradiation, uses Keithley 2410 model instrument to survey electric current and voltage, obtains I-V curve (Fig. 1);
The methylamino bismuth iodide film obtained by the method for the invention uses Shimadzu solidspec3700 model instrument to carry out surface diffuse reflectance test, the modal data that is absorbed (Fig. 2, Fig. 4-Fig. 6);
The methylamino bismuth iodide film obtained by the method for the invention uses Brooker D8 model X-ray diffractometer to carry out material phase analysis test, obtains phase structure figure (Fig. 3).

Claims (4)

1. the preparation method of a methylamino bismuth iodide photovoltaic film, it is characterized in that the method with methylamine, hydroiodic acid, bismuth iodide for raw material, use sol-gal process, by controlling solution concentration and heating time, obtain methylamino bismuth iodide film, concrete operations follow these steps to carry out:
A, be that 1:1-1.5 mix in molar ratio by methylamine and hydroiodic acid, react in DEG C environment of low temperature-10 DEG C-10, time 1-2h, then heat up 50 DEG C-70 DEG C evaporations, obtains powder, re-use absolute ethyl alcohol by powder heating for dissolving, temperature 30 DEG C-80 DEG C, then cool to-30-0 DEG C and separate out methylamine iodine, repetitive operation 2 times, purification methylamine iodine, the finally DEG C heating evaporation in temperature 50 C-70, drying, obtains methylamine iodine powder, collects stand-by;
B, the methylamine iodine powder obtained in step a to be dissolved in organic solvent be that in dimethyl formamide or gamma-butyrolacton, stirring at room temperature, is configured to the methylamine iodine solution that concentration is 0.3-1.5mol/L, is placed in beaker;
Bismuth iodide adds in the methylamine iodine solution of gained in step b by c, in molar ratio 1.5-3:1, is configured to the solution of concentration 0.1-0.5mol/L, adds thermal agitation, and solution is clarified;
D, get step c gained solution and drop on tin oxide transparent conductive glass, tin indium oxide transparent conductive glass or the Si sheet that substrate is doped with fluorine, use the spin coating 10-20 seconds under the rotating speed of 2000-4000r/min of spin coating instrument;
E, by steps d gained sample being placed on temperature control platform, at temperature 100-150 DEG C, heat 5-10min, namely obtain methylamino bismuth iodide film.
2. the preparation method of methylamino bismuth iodide photovoltaic film according to claim 1, is characterized in that in step a, reaction temperature is 0 DEG C.
3. the preparation method of methylamino bismuth iodide photovoltaic film according to claim 1, is characterized in that in step a, methylamine iodine Precipitation Temperature is-10 DEG C--20 DEG C.
4. the preparation method of methylamino bismuth iodide photovoltaic film according to claim 1, is characterized in that evaporating temperature 60 DEG C in step a.
CN201510173613.XA 2015-04-13 2015-04-13 Preparing method of methyl amino bismuth iodide photovoltaic film Pending CN104752065A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820055A (en) * 2016-01-25 2016-08-03 湖北大学 Methyl amino lead iodide bismuth perovskite crystal light absorption layer material and preparation method thereof
CN106008327A (en) * 2016-05-05 2016-10-12 中国计量大学 Organic and inorganic hybrid bismuth and iodine anionic cluster-based semiconductor material
CN106065494A (en) * 2016-06-07 2016-11-02 中国科学院新疆理化技术研究所 A kind of synthetic method of morphology controllable organic inorganic hybridization bismuthino crystal
CN106601917A (en) * 2016-12-02 2017-04-26 广州光鼎科技有限公司 Preparation method of lead-free organic and inorganic cation common hybridization perovskite material and film thereof
CN107815701A (en) * 2017-10-26 2018-03-20 太原理工大学 A kind of electrochemical preparation method of nano-sheet fluorination bismuth thin film and its application

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CN104362253A (en) * 2014-10-23 2015-02-18 河北工业大学 All solid state perovskite microcrystalline silicon composite solar battery and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105820055A (en) * 2016-01-25 2016-08-03 湖北大学 Methyl amino lead iodide bismuth perovskite crystal light absorption layer material and preparation method thereof
CN106008327A (en) * 2016-05-05 2016-10-12 中国计量大学 Organic and inorganic hybrid bismuth and iodine anionic cluster-based semiconductor material
CN106008327B (en) * 2016-05-05 2018-10-02 中国计量大学 A kind of organic inorganic hybridization bismuth iodine anion cluster base semiconductor material
CN106065494A (en) * 2016-06-07 2016-11-02 中国科学院新疆理化技术研究所 A kind of synthetic method of morphology controllable organic inorganic hybridization bismuthino crystal
CN106065494B (en) * 2016-06-07 2018-09-18 中国科学院新疆理化技术研究所 A kind of synthetic method of morphology controllable hybrid inorganic-organic bismuthino crystal
CN106601917A (en) * 2016-12-02 2017-04-26 广州光鼎科技有限公司 Preparation method of lead-free organic and inorganic cation common hybridization perovskite material and film thereof
CN107815701A (en) * 2017-10-26 2018-03-20 太原理工大学 A kind of electrochemical preparation method of nano-sheet fluorination bismuth thin film and its application

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Application publication date: 20150701