CN102603202A - Method for preparing tin selenide photoelectric thin film - Google Patents

Method for preparing tin selenide photoelectric thin film Download PDF

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Publication number
CN102603202A
CN102603202A CN2012100625776A CN201210062577A CN102603202A CN 102603202 A CN102603202 A CN 102603202A CN 2012100625776 A CN2012100625776 A CN 2012100625776A CN 201210062577 A CN201210062577 A CN 201210062577A CN 102603202 A CN102603202 A CN 102603202A
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thin film
substrate
film
preparing
precursor thin
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CN2012100625776A
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刘科高
孙齐磊
纪念静
石磊
许斌
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Shandong Jianzhu University
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Shandong Jianzhu University
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    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a method for preparing a tin selenide photoelectric thin film material, belonging to the technical field of photoelectric thin film preparation. The method comprises the following steps: firstly washing a chip, then putting SnCl2.2H2O and SeO2 into solvents, obtaining a precursor thin film on the chip by a spin coating method and drying the precursor thin film, putting the precursor thin film into a closed container with diamide hydrate, ensuring the precursor thin film sample not to be contacted with diamide hydrate, heating the closed container filled with the precursor thin film sample, taking out the sample and cooling and drying the sample, thus obtaining the tin selenide photoelectric thin film. The method has the following beneficial effects: the method dispenses with the conditions of high temperature and high vacuum, has low requirements for apparatuses, is low in production cost and high in production efficiency and is easy to operate; the tin selenide photoelectric thin film has better continuity and uniformity; the components and structure of the target product are easy to control by the new process; and the production method which is low in cost and can realize industrialization is provided for preparing the tin selenide photoelectric thin film with high performance.

Description

A kind of method for preparing the Tin diselenide optoelectronic film
Technical field
The invention belongs to the optoelectronic film preparing technical field, relate in particular to a kind of method for preparing the Tin diselenide optoelectronic film.
Background technology
Along with society and expanding economy; China's total energy consumption increases severely; The pollution that the energy scarcity and the consumption energy bring has become the outstanding problem in the domestic social development, and therefore developing clean energy all has important meaning to protecting environment, sustainable economic development and constructing harmonious society.In order to utilize the renewable resources of this cleaning of sun power, safety and environmental protection more fully, the research and development of photovaltaic material in recent years comes into one's own day by day.
Tin diselenide is a kind of important IV-VI family semi-conductor, and its indirect band gap is 0.90eV, and direct band gap is 1.30eV, can absorb the overwhelming majority of solar spectrum., environmental friendliness abundant as a kind of content and chemically stable semiconductor material, Tin diselenide is one of potential candidate material of novel solar battery.
The preparation method of SnSe mainly contains chemical vapour deposition, electrochemical method, molecular beam epitaxy, solvent-thermal method, pulsed laser deposition, chemical bath deposition etc. at present.Because raw materials cost is lower, be a kind of very rising optoelectronic thin film material therefore, but existing operational path is complicated, preparation cost is high, thereby need explores preparation technology cheaply equally.This experiment adopts spin coating-chemical co-reducing process to prepare the Tin diselenide optoelectronic film.
As method noted earlier, other method also has different defects.Relevant with the present invention also have following document:
[1]Nicolas?D.Boscher,Claire?J.Carmalt,Robert?G.Palgrave,Ivan?P.Parkin,Atmospheric?pressure?chemical?vapour?deposition?of?SnSe?and?SnSe 2?thin?films?on?glass,Thin?Solid?Films?516(2008)4750-4757.
Reported that mainly the method with chemical vapour deposition has successfully been prepared SnSe and SnSe on glass substrate under normal pressure 2Film.
[2]Biljana?Pejova,Ivan?Grozdanov,Chemical?synthesis,structural?and?optical?properties?of?quantum?sized?semiconducting?tin(II)selenide?in?thin?film?form,Thin?Solid?Films?515(2007)5203-5211.
What mainly tell about is the synthetic SnSe optoelectronic semiconductor film of chemical process, and the structure properties of film is studied.
[3]Dipankar?Giri,Kalyan?Kumar?Das.Theoretical?studies?of?the?electronic?spectrum?of?SnSe.Chemical?Physics?Letters?411(2005),144-149.
Theoretical investigation to the electronic spectrum of SnSe has mainly been described.
[4]R.Indirajith,T.P.Srinivasan,K.Ramamurthi,R.Gopalakrishnan,Synthesis,deposition?and?characterization?of?tin?selenide?thin?films?by?thermal?evaporation?technique,Current?Applied?Physics?10(2010)1402-1406.
Mainly reported in low temperature (being lower than 100 ℃), prepared the SnSe film with simple thermal evaporation techniques, and studied its photoelectric properties.
[5]Ajay?Agarwal,Sunil?H.Chaki,D.Lakshminarayana,Growth?and?thermal?studies?of?SnSe?single?crystals,Materials?Letters?61(2007)5188-5190.
Mainly described monocrystalline, and measured crystalline percent crystallinity, lattice parameter etc. with open steam transportation technology (DVT) preparation SnSe.
[6]A.Lukinskas,V.Jasulaitien,P.Lukinskas,I.Savickaja,P.Kalinauskas,Electrochemical?formation?of?nanometric?layers?oftin?selenides?on?Ti?surface,Electrochimica?Acta?51(2006)6171-6178.
Mainly described with electrochemical method in metal Ti surface deposition SnS nanometer layer, and studied the influence of sedimentation potential the nanometer layer composition.
Summary of the invention
The present invention is in order to solve the deficiency of prior art, and invented a kind of diversely with preparation method prior art, and the Tin diselenide solar cell is with the preparation technology of thin-film material.
The present invention adopts spin coating-chemical co-reducing process to prepare the Tin diselenide thin-film material, and adopting soda-lime glass sheet, silicon chip is substrate, with SnCl 22H 2O and SeO 2Be raw material; The mixture of one or more in deionized water, ethanol, thanomin, the hydrochloric acid is a solvent; Earlier prepare the precursor thin-film of certain thickness Tin diselenide (stoichiometric ratio is SnSe) with spin-coating method; With the hydrazine hydrate is reductive agent, and heating at a lower temperature in encloses container makes precursor thin-film reduce concurrent intercrescence and becomes reaction to obtain title product.
Concrete preparation method of the present invention comprises the step of following order:
A. carrying out the cleaning of substrate, is that 2mm * 2mm glass substrate or silicon substrate are put into trichloromethane by volume with size: the solution of ethanol=5: 1, ultrasonic cleaning 30min; Again substrate is put into acetone: the solution of zero(ppm) water=5: 1, ultrasonic cleaning 30min; In zero(ppm) water, substrate is used ultra-sonic oscillation 30min again; The above-mentioned substrate that obtains is emitted on sends in the glass dish in the baking oven, 100 ℃ down oven dry supply the system film to use.
B. with SnCl 22H 2O and SeO 2Put into solvent, make the material uniform mixing in the solution.Specifically, can be with 1.5~2.5 parts of SnCl 22H 2O, 0.8~1.5 part of SeO 2Put into 25~100 parts solvent, make the material uniform mixing in the solution, wherein solvent is one or more the mixture in deionized water, ethanol, thanomin, the hydrochloric acid.
C. make the outside evenly substrate of the said solution of application step b, and oven dry, the precursor thin-film sample obtained.Can above-mentioned solution be dripped on the substrate that is placed on the sol evenning machine; Restart sol evenning machine with 200~3500 rev/mins of rotation certain hours; Make on dripping solution coat evenly after, 100 ℃ substrate dried after, repeat once more to drip and dry again after going up aforementioned solution and spin coating; So repeat 2~10 times, so on substrate, obtained certain thickness precursor thin-film sample.
D. step c gained precursor thin-film sample is placed on the support, but put into the encloses container of hydrazine hydrate, the precursor thin-film sample is not contacted with hydrazine.It is 15.0~25.0 parts that hydrazine hydrate is put into.The above-mentioned encloses container that the precursor thin film sample is housed is put into baking oven, be heated between 160~220 ℃, soaking time 10~20 hours, cool to room temperature takes out then.
E. with the steps d products therefrom, carry out seasoning after, promptly obtain the Tin diselenide optoelectronic film;
The present invention does not need the high temperature high vacuum condition, and low to the plant and instrument requirement, production cost is low, and production efficiency is high, easy handling.Gained Tin diselenide optoelectronic film has continuity and homogeneity preferably, and the composition and the structure of the easy controlled target product of this novel process are for preparing the method that high performance Tin diselenide optoelectronic film provides a kind of low cost, can realize large-scale industrial production.
Description of drawings
Accompanying drawing 1 is the once XRD figure spectrums of back gained Tin diselenide film of 200 ℃ of reactions in following 20 hours, and the solvent of precursor solution is an ethanol, and substrate is a silicon chip.
Embodiment
Embodiment 1
A. the cleaning of substrate: (size is 2mm * 2mm) to clean silicon substrate as previously mentioned.
B. with 2.036 parts of SnCl 22H 2O and 1.0 parts of SeO 2Put into vial, add 54.545 parts of ethanol, utilize more than the ultrasonic vibration 30min, make the material uniform mixing in the solution.
C. above-mentioned solution is dripped on the silicon substrate that is placed on the sol evenning machine, restart sol evenning machine, sol evenning machine rotated 5 seconds with 200 rev/mins; With 1000 rev/mins of rotations 15 seconds; Make on dripping solution coat evenly after, 100 ℃ substrate dried after, repeat once more to drip and dry again after going up aforementioned solution and spin coating; So repeat 8 times, so on substrate, obtained certain thickness precursor thin-film sample.
D. the precursor thin-film sample of above-mentioned technology gained is put into sealable container; And put into 18.182 parts of hydrazine hydrates; The precursor thin film sample places it is not contacted with hydrazine, and the encloses container that the precursor thin film sample is housed is put into baking oven, is heated to 200 ℃; Soaking time 20 hours, cool to room temperature takes out then.
E. with above-mentioned steps d product, carry out seasoning after, promptly obtain the Tin diselenide optoelectronic film;
Embodiment 2
A. the cleaning of substrate: (size is 2mm * 2mm) to clean silicon substrate as previously mentioned.
B. with 2.036 parts of SnCl 22H 2O and 1.0 parts of SeO 2Put into vial, add 54.545 parts of ethanol, utilize more than the ultrasonic vibration 30min, make the material uniform mixing in the solution.
C. above-mentioned solution is dripped on the silicon substrate that is placed on the sol evenning machine, restart sol evenning machine, sol evenning machine rotated 5 seconds with 200 rev/mins; With 3000 rev/mins of rotations 15 seconds; Make on dripping solution coat evenly after, 100 ℃ substrate dried after, repeat once more to drip and dry again after going up aforementioned solution and spin coating; So repeat 8 times, so on silicon substrate, obtained certain thickness precursor thin-film sample.
D. the precursor thin-film sample of above-mentioned technology gained is put into sealable container; And put into 18.182 parts of hydrazine hydrates; The precursor thin film sample places it is not contacted with hydrazine, and the encloses container that the precursor thin film sample is housed is put into baking oven, is heated to 180 ℃; Soaking time 20 hours, cool to room temperature takes out then.
E. with the steps d products therefrom, carry out seasoning after, promptly obtain the Tin diselenide optoelectronic film.

Claims (5)

1. method for preparing the Tin diselenide optoelectronic film comprises the step of following order:
A. the cleaning of glass or silicon substrate;
B. with 1.5~2.5 parts of SnCl 22H 2O, 0.8~1.5 part of SeO 2Put into 25~100 parts solvent, make the material uniform mixing in the solution;
C. make the outside evenly substrate of the said solution of application step b, and oven dry, the precursor thin-film sample obtained;
D. step c gained precursor thin-film sample is placed on the support; But put into the encloses container of hydrazine hydrate; The precursor thin-film sample is not contacted with hydrazine, the encloses container that the precursor film sample is housed is put into baking oven, be heated between 160~220 ℃; Soaking time 10~20 hours, cool to room temperature takes out then;
E. with the steps d products therefrom, carry out seasoning, obtain the Tin diselenide optoelectronic film.
2. a kind of method for preparing the Tin diselenide optoelectronic film as claimed in claim 1 is characterized in that, the said cleaning of step a is to be 2mm * 2mm glass substrate or silicon substrate with size, puts into the volume ratio trichloromethane: the solution of ethanol=5: 1, ultrasonic cleaning; Again substrate is put into acetone: the solution of zero(ppm) water=5: 1, ultrasonic cleaning; In zero(ppm) water, substrate is used ultra-sonic oscillation again; The above-mentioned substrate that obtains is emitted on sends in the baking oven oven dry in the glass dish and supply the system film to use.
3. a kind of method for preparing the Tin diselenide optoelectronic film as claimed in claim 1 is characterized in that, the said solvent of step b is at least a in deionized water, ethanol, thanomin, the hydrochloric acid.
4. a kind of method for preparing the Tin diselenide optoelectronic film as claimed in claim 1; It is characterized in that the substrate of the said even coating of step c is through the sol evenning machine spin coating; Sol evenning machine is with 200~3500 rev/mins of rotations; After then substrate being dried, so repeat once more 2~10 times, obtained certain thickness precursor thin-film sample.
5. a kind of method for preparing the Tin diselenide optoelectronic film as claimed in claim 1 is characterized in that, puts into 15.0~25.0 parts of hydrazine hydrates in the said encloses container of steps d.
CN2012100625776A 2012-03-12 2012-03-12 Method for preparing tin selenide photoelectric thin film Pending CN102603202A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193505A (en) * 2013-03-26 2013-07-10 太原理工大学 Preparation method of photonic crystal concave thin-film in titanium dioxide/silver core-shell structure
CN105097989A (en) * 2014-06-13 2015-11-25 山东建筑大学 Method for preparing zinc sulfide photoelectric film
CN105439106A (en) * 2015-12-17 2016-03-30 山东建筑大学 Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate
CN105552205A (en) * 2015-12-17 2016-05-04 山东建筑大学 Method for preparing bismuth selenide thermoelectric film from bismuth chloride
CN105576114A (en) * 2015-12-17 2016-05-11 山东建筑大学 Method for preparing bismuth selenide thermoelectric film by use of bismuth acetate
CN106744727A (en) * 2016-11-28 2017-05-31 福建师范大学 Screw dislocation drives the preparation method of growth spiral type stratiform stannic selenide nanometer sheet
CN108878557A (en) * 2018-07-01 2018-11-23 山东建筑大学 A method of copper and iron selenium conductive film is prepared with chloride
CN109023483A (en) * 2018-06-29 2018-12-18 洛阳师范学院 A kind of selenizing tin thin film and preparation method thereof
CN112113669A (en) * 2020-08-28 2020-12-22 哈尔滨工业大学 Fish scale-shaped hollow SnSe nanotube self-powered infrared detector and preparation method thereof

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CN101412505A (en) * 2008-09-05 2009-04-22 山东建筑大学 Preparation of high-purity tin diselenide nano-plate
CN101630701A (en) * 2008-12-03 2010-01-20 山东建筑大学 Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell

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CN101630701A (en) * 2008-12-03 2010-01-20 山东建筑大学 Method for preparing copper-indium-selenium optoelectronic thin film material of solar cell

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193505B (en) * 2013-03-26 2014-09-24 太原理工大学 Preparation method of photonic crystal concave thin-film in titanium dioxide/silver core-shell structure
CN103193505A (en) * 2013-03-26 2013-07-10 太原理工大学 Preparation method of photonic crystal concave thin-film in titanium dioxide/silver core-shell structure
CN105097989A (en) * 2014-06-13 2015-11-25 山东建筑大学 Method for preparing zinc sulfide photoelectric film
CN105576114B (en) * 2015-12-17 2018-05-15 山东建筑大学 A kind of method that bismuth selenide thermal electric film is prepared with bismuth acetate
CN105439106A (en) * 2015-12-17 2016-03-30 山东建筑大学 Method for preparing bismuth selenide thermoelectric thin film with bismuth sulfate
CN105552205A (en) * 2015-12-17 2016-05-04 山东建筑大学 Method for preparing bismuth selenide thermoelectric film from bismuth chloride
CN105576114A (en) * 2015-12-17 2016-05-11 山东建筑大学 Method for preparing bismuth selenide thermoelectric film by use of bismuth acetate
CN105552205B (en) * 2015-12-17 2018-05-11 山东建筑大学 A kind of method that bismuth selenide thermal electric film is prepared with bismuth chloride
CN106744727A (en) * 2016-11-28 2017-05-31 福建师范大学 Screw dislocation drives the preparation method of growth spiral type stratiform stannic selenide nanometer sheet
CN109023483A (en) * 2018-06-29 2018-12-18 洛阳师范学院 A kind of selenizing tin thin film and preparation method thereof
CN108878557A (en) * 2018-07-01 2018-11-23 山东建筑大学 A method of copper and iron selenium conductive film is prepared with chloride
CN112113669A (en) * 2020-08-28 2020-12-22 哈尔滨工业大学 Fish scale-shaped hollow SnSe nanotube self-powered infrared detector and preparation method thereof
CN112113669B (en) * 2020-08-28 2021-08-13 哈尔滨工业大学 Fish scale-shaped hollow SnSe nanotube self-powered infrared detector and preparation method thereof

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Application publication date: 20120725