CN102963936A - Preparation method of gamma-MnS thin film with branch-shaped structure - Google Patents
Preparation method of gamma-MnS thin film with branch-shaped structure Download PDFInfo
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- CN102963936A CN102963936A CN2012104581758A CN201210458175A CN102963936A CN 102963936 A CN102963936 A CN 102963936A CN 2012104581758 A CN2012104581758 A CN 2012104581758A CN 201210458175 A CN201210458175 A CN 201210458175A CN 102963936 A CN102963936 A CN 102963936A
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Abstract
The invention provides a preparation method of a gamma-MnS thin film with a branch-shaped structure, comprising the following steps of: adding manganese salt into deionized water to obtain solution A; adding thioacetamide into the solution A to obtain solution B; adjusting the pH value of the solution B to 7.5-8.5 to obtain solution C; pouring the solution C into a microwave hydrothermal reaction kettle, vertically putting an ITO (indium tin oxide) substrate into the reaction kettle, sealing the reaction kettle, putting the sealed reaction kettle into a warm-pressing double-control microwave hydrothermal reaction instrument, carrying out reaction by selecting a temperature-control mode, and naturally cooling to room temperature after the reaction; and opening the reaction kettle, taking out the substrate, washing the substrate by distilled water, and drying in a vacuum drying box to obtain the gamma-MnS thin film with the branch-shaped structure. According to the preparation method, the simple microwave hydrothermal method is adopted, the preparation method is completed in a sealed liquid-phase environment by one step, and the preparation method is short in reaction period, free from environment pollution, simple in technology, easy to operate, and low in energy consumption. The prepared thin film has the homogeneous branch-shaped structure, and is compact in structure, high in crystallinity, and less in defects, and the adopted raw materials are low in price, easy to obtain, and low in cost.
Description
Technical field
The present invention relates to a kind of manganese sulfide thin film technology method, be specifically related to a kind of dendritic structure γ-MnS thin film technology method.
Background technology
Metallic sulfide is the important semiconductor material of a class, is widely used in fields such as optics, photocell, energy medium for storing and catalysis.MnS is the weak magnetic semiconductor of VII B-VI A, band gap width is 3.7eV, window/cushioning material at the preparation solar cell, the short wavelength light electrical part, catalytic material, there is potential application [ki s J the aspects such as mass optical memory, Tang K B, Yang Q, et a1.Solvothermalsynthesis of metastable γ-MnS hollow spheres and control of their phase[J] .Eur Jlnorg Chem, 2005:4124-4128.] MnS generally has 3 kinds of phases, i.e. octahedral coordinations, green stable rock salt structure α-MnS (RS); Tetrahedral coordination, pink colour steady zincblende lattce structure β-MnS and the wurtzite structure γ-MnS that be situated between.Metastable β and γ-MnS are at 100-400 ℃ of α-MnS that easily changes stable state into, and this transformation is irreversible.Metastable MnS compares with the MnS of stable state, has shown more special chemical property, electric property, optical property and magnetic performance.Therefore preparing single-phase metastable state MnS becomes research focus.
At present, the method for preparing the manganese sulfide film mainly contains continuous ionic layer absorption reaction method (SlLAR) [H.M.Pathan, S.S.Kale, C.D.Lokhande, etal.Preparation and characterization of amorphousmanganese sulfide thin flms by SlLAR method[J] .Materials Research Bulletin.2007,42:1565-1569.], chemical Vapor deposition process [Selective Deposition of Ruthenium Films byDigital CVD[J] .Chemical Vapor Deposition, 2005,11 (2): 94-98.], radio frequency sputtering method [I.Oidor-Juarez, P.Garcla-Jimenez, G.Torres-Delgado, et al.Substrate temperatureeffects on the growth and properties of γ-MnS thin films grown by rf sputtering[J] .Materials Research Bulletin, 2002,37:1749-1754.], molecular beam epitaxy [K.A.Prior, C.Bradford, L.David, et al.Metastable group II sulphides grown by MBE:surfacemorphology and crystal structure[J] .Journal of Crystal Growth, 2005,275:141-149.], chemical bath deposition method [C.G ü m ü s, C.ulutas, R.Esen, et a1.Preparation andcharacterization of crystalline MnS thin films by chemical bath deposition[J] .ThinSolid Films, 2005,492:1-5.] etc.Yet there are a lot of shortcomings in these methods, usually need special instrument, perhaps need strict experiment condition and long reaction times.As adopt continuous ionic layer absorption reaction experimental implementation complicated difficult with control and the preparation film be amorphous; Though the film quality of chemical Vapor deposition process and radio frequency sputtering method preparation is good but the desired apparatus expensive of the method and employed source of the gas have severe toxicity; Adhesive force by simple chemical bath deposition preparation is relatively poor.The drawback of above method is so that seek a kind of easy handling, environmental friendliness and with low cost, and the simple method of equipment seems particularly important.
Summary of the invention
The objective of the invention is to propose a kind of reaction time short, temperature of reaction is low, environmental friendliness, with low cost, and simple to operate, reaction can be in liquid phase a step finish, good reproducibility does not need the thermal treatment in later stage just can obtain good crystallinity, surfacing, densification, dendritic structure γ that defective is few-MnS thin film technology method.
For achieving the above object, the technical solution used in the present invention is:
1) the analytical pure manganese salt with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.01mol/L-0.1mol/L;
2) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.02mol/L-0.3mol/L gets solution B;
3) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 7.5-8.5, gets solution C;
4) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 40%-65%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 120-180 ℃, and the reaction times is controlled at 60min-180min, and reaction naturally cools to room temperature after finishing;
5) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 40-80 ℃ vacuum drying oven subsequently.
Described manganese salt is Manganous chloride tetrahydrate or manganese acetate.
Described ito substrate is through steps of processing: be placed on ito glass substrate in the distilled water and use ultrasonic oscillation 20-50min, then ito substrate is immersed in 24-72h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 50-80 ℃ baking oven.
The mixing solutions of described hydrogen peroxide and concentrated nitric acid is that hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid.
Useful effect:
The present invention adopts simple microwave-hydrothermal method, a step finishes in airtight liquid phase environment, and reaction time is short, and is free from environmental pollution, the simple easy handling of technique, energy consumption is low, and prepared film morphology is the dendritic structure of homogeneous, compact structure, crystallization degree is high, defective is few, and the raw material that adopts is cheap to be easy to get, and cost is low.
Description of drawings
Fig. 1 and Fig. 2 are respectively XRD figure and the SEM figure of the film that embodiment 1 prepares take manganese acetate as the manganese source;
Fig. 3 and Fig. 4 are respectively XRD figure and the SEM figure of the film that embodiment 2 prepares take Manganous chloride tetrahydrate as the manganese source.
Embodiment
Embodiment 1:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 20min, then ito substrate is immersed in 24h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 50 ℃ baking oven.
2) the analytically pure manganese acetate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.01mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.02mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 7.5, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 40%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 180 ℃, and the reaction times is controlled at 60min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 40 ℃ vacuum drying oven subsequently.
The film of preparation is γ-MnS film as can be seen from Figure 1, and it has dendritic structure as can be seen from Figure 2.
Embodiment 2:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 25min, then ito substrate is immersed in 30h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 55 ℃ baking oven.
2) the analytically pure Manganous chloride tetrahydrate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.03mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.06mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 7.8, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 50%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 160 ℃, and the reaction times is controlled at 120min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 45 ℃ vacuum drying oven subsequently.
The film of preparation is γ-MnS film as can be seen from Figure 3, and it has dendritic structure as can be seen from Figure 4.
Embodiment 3:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 30min, then ito substrate is immersed in 40h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 60 ℃ baking oven.
2) the analytically pure manganese acetate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.05mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.12mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 8.0, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 45%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 150 ℃, and the reaction times is controlled at 140min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 50 ℃ vacuum drying oven subsequently.
Embodiment 4:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 35min, then ito substrate is immersed in 50h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 65 ℃ baking oven.
2) the analytically pure Manganous chloride tetrahydrate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.08mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.18mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 8.3, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 55%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 140 ℃, and the reaction times is controlled at 150min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 60 ℃ vacuum drying oven subsequently.
Embodiment 5:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 40min, then ito substrate is immersed in 68h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 70 ℃ baking oven.
2) the analytically pure manganese acetate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.07mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.21mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 8.2, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 62%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 130 ℃, and the reaction times is controlled at 160min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 70 ℃ vacuum drying oven subsequently.
Embodiment 6:
1) is placed on ito glass substrate in the distilled water and uses ultrasonic oscillation 50min, then ito substrate is immersed in 72h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wherein, hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 80 ℃ baking oven.
2) the analytically pure Manganous chloride tetrahydrate with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.1mol/L;
3) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.3mol/L gets solution B;
4) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 8.5, gets solution C;
5) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 65%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 120 ℃, and the reaction times is controlled at 180min, and reaction naturally cools to room temperature after finishing;
6) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure γ-MnS film in 80 ℃ vacuum drying oven subsequently.
Claims (4)
1. dendritic structure y-MnS thin film technology method is characterized in that may further comprise the steps:
1) the analytical pure manganese salt with solubility joins in the deionized water, and making manganese ion concentration is the clear solution A of 0.01mol/L-0.1mol/L;
2) in A solution, add analytically pure thioacetamide (CH
3CSNH
2), make the CH in the solution
3CSNH
2Concentration is that 0.02mol/L-0.3mol/L gets solution B;
3) the pH value that adds the NaOH regulator solution of 2mol/L in the B solution is 7.5-8.5, gets solution C;
4) prepared solution C is poured in the microwave hydrothermal reaction kettle, compactedness is 40%-65%, then ito substrate is vertically put into reactor, put it into after the sealing in the warm-pressing double-control microwave hydrothermal reaction, select temperature control mode to react, temperature of reaction is controlled at 120-180 ℃, and the reaction times is controlled at 60min-180min, and reaction naturally cools to room temperature after finishing;
5) open reactor, take out substrate, use the distilled water flushing substrate, drying obtains dendritic structure y-MnS film in 40-80 ℃ vacuum drying oven subsequently.
2. dendritic structure y-MnS thin film technology method according to claim 1, it is characterized in that: described manganese salt is Manganous chloride tetrahydrate or manganese acetate.
3. dendritic structure y-MnS thin film technology method according to claim 1, it is characterized in that: described ito substrate is through steps of processing: be placed on ito glass substrate in the distilled water and use ultrasonic oscillation 20-50min, then ito substrate is immersed in 24-72h in the mixing solutions of hydrogen peroxide and concentrated nitric acid, wash 3-5 time respectively with distilled water and dehydrated alcohol after taking out, dry in 50-80 ℃ baking oven.
4. dendritic structure y-MnS thin film technology method according to claim 3, it is characterized in that: the mixing solutions of described hydrogen peroxide and concentrated nitric acid is that hydrogen peroxide mixes by the volume ratio of 8:1 with concentrated nitric acid.
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|---|---|---|---|---|
| CN104362327A (en) * | 2014-11-10 | 2015-02-18 | 常开军 | High-purity battery-level manganese source and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN101527261A (en) * | 2009-02-16 | 2009-09-09 | 大连理工大学 | Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film |
| CN102560674A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of copper sulfide thin film with x-shaped-flaky crystal crossing structure |
| CN102583556A (en) * | 2012-03-07 | 2012-07-18 | 陕西科技大学 | Preparation method of pencil-shaped gamma-MnS microcrystal |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101527261A (en) * | 2009-02-16 | 2009-09-09 | 大连理工大学 | Hydro-thermal treatment method capable of improving performance of chalcogen semiconductor film |
| CN102560674A (en) * | 2011-11-23 | 2012-07-11 | 陕西科技大学 | Preparation method of copper sulfide thin film with x-shaped-flaky crystal crossing structure |
| CN102583556A (en) * | 2012-03-07 | 2012-07-18 | 陕西科技大学 | Preparation method of pencil-shaped gamma-MnS microcrystal |
Non-Patent Citations (2)
| Title |
|---|
| 《人工晶体学报》 20120430 辛宇等 pH值对微波水热法制备gamma-MnS微晶形貌及光学性能的影响 第312-317页 1-4 第41卷, 第2期 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104362327A (en) * | 2014-11-10 | 2015-02-18 | 常开军 | High-purity battery-level manganese source and preparation method thereof |
| CN104362327B (en) * | 2014-11-10 | 2016-06-15 | 湖北高博科技有限公司 | A kind of high purity battery level manganese source and preparation method thereof |
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Application publication date: 20130313 |