CN100545081C - Dendritic silver selenide nano crystal thin film material and preparation method - Google Patents
Dendritic silver selenide nano crystal thin film material and preparation method Download PDFInfo
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- CN100545081C CN100545081C CNB2007100527217A CN200710052721A CN100545081C CN 100545081 C CN100545081 C CN 100545081C CN B2007100527217 A CNB2007100527217 A CN B2007100527217A CN 200710052721 A CN200710052721 A CN 200710052721A CN 100545081 C CN100545081 C CN 100545081C
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Abstract
A kind of dendritic silver selenide nano crystal thin film material and preparation method.The method for making of this material is the base material with metal silver surface, the simple substance selenium powder, and organic alcohol solvent places the tetrafluoroethylene reactor altogether, 120 ℃-180 ℃ reactions down, metal silver surface original position at base material makes the thin-film material of being made up of the selenide nanocrystal of dendritic structure, and reaction naturally cools to room temperature after finishing, product cleans with dehydrated alcohol, and is dry below 50 ℃.Described base material is meant the argent paillon foil, and semi-conductor silicon chip, conductive glass ITO of one deck nanometer metallic silver etc. plated on the surface; The present invention goes on foot directly growth in situ selenide nanocrystal film in the substrate with metal silver surface of chemical reaction by one, uses the simplest organic alcohol as reaction medium, environmental friendliness; Of no use to any additive and tensio-active agent, do not need subsequent purification step and crystal formation perfection; Reaction is quick, and is easy to operate, has the wide industrial application prospect.
Description
Technical field:
The invention belongs to material chemistry technical field, relate in particular to a kind of chemical process for preparing dendritic silver selenide nano crystal thin film material.
Background technology:
Silver selenide (Ag
2Se) crystal is a kind of A
I 2B
VIThe semiconductor material of type is because its distinctive electricity and optical property receive researchist's concern for many years always.At present, this material has been widely used in numerous areas such as solar cell, fuel cell, electrochemistry of solids transmitter, magnetic transducing device and spectral filter, is with a wide range of applications.The silver selenide crystal has high temperature phase (α-Ag
2Se) with low temperature (β-Ag mutually
2Se) two kinds of phases, the transition temperature between two phases is 133 degrees centigrade.α-the Ag of body-centered cubic structure
2Se is a kind of ionic conductor material, is widely used in photoelectricity secondary cell industry at present; β-the Ag of orthohormbic structure
2Se has narrower band gap, can be used as photochromics and thermochromic material that the photo imaging is used.
In recent years, the existing many reports of silver selenide crystalline preparation method comprise the high energy ball mill method, microwave irradiation, sonochemical method, microemulsion micelle assay, electrolytic process and molecule precursor method etc.But these methods usually rely on harsh preparation condition just can carry out, and needs high temperature, and high pressure perhaps uses the high organometallic reagent of toxicity, and the bigger organic solvent (triphenylphosphine, hydrazine hydrate) of toxicity etc.Post-processing operation such as purification simultaneously also relatively waste time and energy.Have recently the report point out to use special trigonal-Se as masterplate under the condition of room temperature with AgNO
3Solution effects prepares the method for silver selenide monocrystal nanowire.CN1275525A (embodiment 4) also discloses the method for preparing the silver selenide monocrystal nanowire, this method adds analytically pure simple substance Se in the poly-four atmosphere ethene liner autoclaves with analytically pure silver oxalate, with quadrol is that solvent adds to compactedness 80%, place 140-180 ℃ constant temperature oven internal reaction 6-12 hour, naturally cool to room temperature then, filter and obtain the grey black product; Use anhydrous diethyl ether, deionized water, dilute nitric acid solution and absolute ethanol washing successively, at last product is placed 70 ℃ vacuum drier inner drying 2 hours.The Ag that in quadrol, generates
2The Se powder is pure quadrature phase.SEM shows, synthetic Ag in quadrol
2Se in the form of sheets.The atomic ratio of Ag: Se is 2: 1.05, all meets stoichiometric ratio.Time reaction is carried out the most fully for solvent with the quadrol, and temperature is to Ag
2Synthesizing of Se also has significant effects. and principal phase is Ag in the sample of 140 ℃ of acquisitions
2Se, but also contain a small amount of Se; And in the sample of 160 ℃ of acquisitions, though principal phase also is Ag
2Se but contains a small amount of Ag.
More than mostly be to utilize the compound (Silver Nitrate, silver oxalate etc.) of silver under certain acid-base condition, to react in these improved methods, have some impurity in the reaction product unavoidably and generate.Toxicity such as quadrol as solvent and reaction medium are bigger, are unfavorable for further suitability for industrialized production.In addition, what obtain in the report in the past is powdery product all, also needs further film forming in a lot of the application.Therefore, seek a kind of simple, fast and the method for environmental protection, use low cost raw material under avirulent condition directly preparation silver selenide film material remain researchists and need the problem that solves.
Summary of the invention:
Problem to be solved by this invention is: overcome big, the shortcomings such as product is impure, complex process, conditional request harshness of solvent toxicity that exist in the present preparation silver selenide crystalline method.Provide without any need for template, do not need to add any tensio-active agent, needn't can make the method for highly purified dendritic silver selenide nano crystal thin film material through loaded down with trivial details post-processing operation such as removal of impurities.In addition, this invention allows to pass through directly growth in situ selenide nanocrystal film in the substrate of various metals, semi-conductor etc. of a step chemical reaction, has the wide industrial application prospect.
The technical scheme that the present invention takes the problem that will solve is:
A kind of selenide nanocrystal material is characterized in that: this material is to have the thin-film material that original position makes on the base material of metal silver surface dendritic silver selenide nano crystal is formed.
A kind of method for preparing the thin-film material of dendritic silver selenide nano crystal composition, it is characterized in that: this method is the base material with metal silver surface, simple substance selenium powder (Se), and organic alcohol solvent places the tetrafluoroethylene reactor altogether, under 120 ℃ of-180 ℃ of temperature direct reaction 3-12 hour, make the thin-film material of selenide nanocrystal composition with dendritic structure in the metal silver surface original position of base material, after reaction finishes, naturally cool to room temperature, final product cleans with dehydrated alcohol, and is dry below 50 ℃.
Described base material with metal silver surface is meant the argent paillon foil, and the surface has been plated semi-conductor silicon chip, the surface of one deck nanometer metallic silver and plated conductive glass ITO of one deck nanometer metallic silver etc.; Described organic alcohol solvent comprises methyl alcohol, ethanol, propyl alcohol, ethylene glycol, lauryl alcohol and phenylcarbinol etc.
The method that plates one deck nanometer metallic silver film at material surfaces such as semi-conductor silicon chip, conductive glass ITO comprises plating, ion sputtering, vapour deposition, electrochemical deposition, silver mirror reaction etc.
The concentration of simple substance selenium powder is 0.0007-0.007 gram selenium/milliliter organic alcohol solvent in the reactant.
The present invention at first will have the base material of metal silver surface, the simple substance selenium powder, and organic alcohol solvent blend in the tetrafluoroethylene reactor, sealing is placed in the retort furnace or desk-top loft drier of temperature programming function, under 120 ℃ of-180 ℃ of temperature direct reaction 3-12 hour, retort furnace or desk-top loft drier temperature rise rate are 2-10 ℃/minute, after reaction finishes, powered-down is cooled to room temperature by reactor in retort furnace or loft drier, or reactor taken out to be put in naturally cools to room temperature in the air.
Advantage of the present invention:
1, with simple organic alcohol as reaction medium, by a step chemical reaction directly metal silver surface (the silver foil sheet, be coated with the argent film semi-conductor, be coated with the materials such as conductive glass of argent film) go up in-situ preparing by the nanocrystalline silver selenide film of forming of dendroid, reaction is quick, easy to operate, as can also to avoid other wet chemistry prepared in reaction to be caused product impure phenomenon.
2, need not to use the bigger solvent of toxicity such as triphenylphosphine, hydrazine hydrate, quadrol and octadecylene etc., belong to environmentally friendly reaction.Simultaneously do not need to use any tensio-active agent such as CTAB etc.Be convenient to suitability for industrialized production and technology popularization.
3, the present invention places reactant the airtight polytetrafluoroethylcontainer container that has stainless steel outer sleeve, reaction under the lower temperature and can be in various substrates direct film forming, thereby overcome the shortcoming of method complex process such as gel method, vapor deposition method, spraying pyrolytic decomposition.
Description of drawings
The electron photomicrograph of the silver selenide nano crystal thin film material of Fig. 1, embodiment 1 preparation
The electron photomicrograph of the silver selenide nano crystal thin film material of Fig. 2, embodiment 2 preparations
The electron photomicrograph of the silver selenide nano crystal thin film material of Fig. 3, embodiment 3 preparations
Embodiment:
Embodiment 1
(1) preparation work: analytical pure argent paillon foil is put into the beaker that fills deionized water, be soaked in the dehydrated alcohol stand-by after 0.5 hour with the ultrasonic cleaner cleaning.Polytetrafluoroethylcontainer container is used tap water, distilled water, absolute ethanol washing successively, and dry back is stand-by.
(2) reactions steps: the argent paillon foil of handling is put into polytetrafluoroethylcontainer container, adding methanol solvate to the height of container 80% also adds selenium powder simultaneously, selenium powder concentration is 0.0007 grams per milliliter, polytetrafluoroethylcontainer container is put into stainless steel outer sleeve and placed the retort furnace with temperature programming function, temperature rise rate is 2 ℃/minute, is warmed up to 160 ℃ of reactions 12 hours.
(3) aftertreatment: reaction is closed the retort furnace power supply and is naturally cooled to room temperature after finishing.With put into after the dehydrated alcohol wash products 3 times vacuum drying oven in 50 ℃ dry 5 hours down, obtain the silver selenide film sample, carefully change over to then in the sample bottle, in lucifuge, exsiccant environment, preserve.Product colour is a grey black, and the microtexture under electron microscope is that dendroid is nanocrystalline.Electron photomicrograph is seen Fig. 1.
Embodiment 2
(1) preparation work: with embodiment 1
(2) reactions steps: the argent paillon foil of handling is put into polytetrafluoroethylcontainer container, adding lauryl alcohol solvent to the height of container 80% also adds selenium powder simultaneously, selenium powder concentration is 0.0014 grams per milliliter, polytetrafluoroethylcontainer container is put into stainless steel outer sleeve and placed the retort furnace with temperature programming function, be warmed up to 180 ℃, reacted 6 hours, temperature rise rate is 10 ℃/minute.
(3) aftertreatment: reaction is closed the retort furnace power supply and is naturally cooled to room temperature after finishing.With put into after the dehydrated alcohol wash products 2 times vacuum drying oven in 50 ℃ dry 4 hours down, obtain the silver selenide film sample, carefully change over to then in the sample bottle, in lucifuge, exsiccant environment, preserve.Product colour is a grey black, and the microtexture under electron microscope is that dendroid is nanocrystalline.Electron photomicrograph is seen Fig. 2.
Embodiment 3
(1) preparation work: the semi-conductor silicon chip that the surface of prepared fresh plating (electrochemical deposition) is had one deck nanometer metallic silver film as reactive group at the bottom of, it is standby to put into vacuum drying oven.Polytetrafluoroethylcontainer container is used tap water, distilled water, absolute ethanol washing successively, and dry back is stand-by.
(2) reactions steps: the semi-conductor silicon chip that the surface is coated with one deck nanometer metallic silver film is put into polytetrafluoroethylcontainer container, adding alcohol solvent to the height of container 80% also adds selenium powder simultaneously, selenium powder concentration is 0.0007 grams per milliliter, polytetrafluoroethylcontainer container is put into stainless steel outer sleeve and place desk-top loft drier with temperature programming function, be warmed up to 140 ℃ of afterreactions of temperature 3 hours, temperature rise rate is 5 ℃/minute.
(3) aftertreatment: reaction is closed desk-top loft drier power supply and is naturally cooled to room temperature after finishing.With put into after the dehydrated alcohol wash products 3 times vacuum drying oven in 50 ℃ dry 4 hours down, obtain the silver selenide film sample, carefully change over to then in the sample bottle, in lucifuge, exsiccant environment, preserve.Its product colour is a grey black, and the microtexture under electron microscope is that dendroid is nanocrystalline.Electron photomicrograph is seen Fig. 3
Embodiment 4
(1) preparation work: the conductive glass (ITO) that the surface of prepared fresh plating (electrochemical deposition) is had one deck nanometer metallic silver film is as at the bottom of the reactive group, and it is standby to put into vacuum drying oven.Polytetrafluoroethylcontainer container is used tap water, distilled water, absolute ethanol washing successively, and dry back is stand-by.
(2) reactions steps: the ITO that surface treated is coated with one deck nanometer metallic silver film puts into polytetrafluoroethylcontainer container, adding alcohol solvent to the height of container 80% also adds selenium powder simultaneously, selenium powder concentration is 0.0007 grams per milliliter, polytetrafluoroethylcontainer container is put into stainless steel outer sleeve and place desk-top loft drier with temperature programming function, be warmed up to 150 ℃ of temperature, reacted 4 hours.Temperature rise rate is 4 ℃/minute.
(3) aftertreatment: reaction is closed desk-top loft drier power supply and is naturally cooled to room temperature after finishing.With put into after the dehydrated alcohol wash products 3 times vacuum drying oven in 50 ℃ dry 4 hours down, obtain the silver selenide film sample, carefully change over to then in the sample bottle, in lucifuge, exsiccant environment, preserve.Its product colour is a grey black, and the microtexture under electron microscope is that dendroid is nanocrystalline.
Embodiment 5
(1) preparation work: with embodiment 4
(2) reactions steps: the ITO that surface treated is coated with one deck nanometer metallic silver film puts into polytetrafluoroethylcontainer container, adding phenylcarbinol solvent to the height of container 80% also adds selenium powder simultaneously, selenium powder concentration is 0.0007 grams per milliliter, polytetrafluoroethylcontainer container is put into stainless steel outer sleeve and place desk-top loft drier with temperature programming function, be warmed up to 120 ℃ of temperature, reacted 8 hours, temperature rise rate is 5 ℃/minute.
(3) aftertreatment: reaction is closed desk-top loft drier power supply and is naturally cooled to room temperature after finishing.With put into after the dehydrated alcohol wash products 2 times vacuum drying oven in 50 ℃ dry 4 hours down, obtain the silver selenide film sample, carefully change over to then in the sample bottle, in lucifuge, exsiccant environment, preserve.Its product colour is a grey black, and the microtexture under electron microscope is that dendroid is nanocrystalline.
The present invention directly adopts simple substance selenium and the base material with metal silver surface to prepare dendritic silver selenide nano crystal thin film material through single step reaction, and uses the simplest organic alcohol solvent as reaction medium.Belong to environmentally friendly reaction.Of no use to any additive and tensio-active agent, do not need subsequent purification step and crystal formation perfection.Reaction is quick, and is easy to operate, is convenient to suitability for industrialized production and technology popularization.Can reduce cost greatly because reduced purifying technique, considerable economic is arranged.
Claims (5)
1, a kind of preparation method of dendritic silver selenide nano crystal thin film material; It is characterized in that: the preparation method is the base material with metal silver surface; The simple substance selenium powder; And organic alcohol solvent places the polytetrafluoroethylene (PTFE) reactor altogether; Under 120 ℃ of-180 ℃ of temperature, directly reacted 3-12 hour; Make the thin-film material of the selenide nanocrystal composition with dendritic structure in the metal silver surface original position of base material; After reaction finishes; Naturally cool to room temperature; End product cleans with absolute ethyl alcohol; Dry below 50 ℃
Described base material with metal silver surface is meant that argent paillon foil, surface plated the conductive glass ITO that one deck nanometer metallic silver has been plated on semiconductor silicon, the surface of one deck nanometer metallic silver; Described organic alcohol solvent comprises methyl alcohol, ethanol, propyl alcohol, lauryl alcohol and phenylcarbinol.
2, the preparation method of dendritic silver selenide nano crystal thin film material according to claim 1 is characterized in that: the method at semiconductor silicon, conductive glass ITO material surface plating one deck nanometer metallic silver film comprises plating, ion sputtering, vapour deposition, electrochemical deposition, silver mirror reaction.
3, dendritic silver selenide nano crystal thin film material according to claim 1 the preparation method, it is characterized in that: the concentration of simple substance selenium powder is 0.0007-0.007 gram selenium/milliliter organic alcohol solvent in the reactant.
4, the preparation method of dendritic silver selenide nano crystal thin film material according to claim 1, it is characterized in that: base material with metal silver surface, the simple substance selenium powder, and organic alcohol solvent places the tetrafluoroethylene reactor altogether, place the retort furnace or the desk-top loft drier of temperature programming function, under 120 ℃ of-180 ℃ of temperature direct reaction 3-12 hour, retort furnace or desk-top loft drier temperature rise rate were 2-10 ℃/minute.
5, the preparation method of dendritic silver selenide nano crystal thin film material according to claim 4, it is characterized in that, after reaction finished, powered-down was cooled to room temperature by reactor in retort furnace or loft drier, or reactor taken out to be put in naturally cooled to room temperature in the air.
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| CN101805136A (en) * | 2010-03-11 | 2010-08-18 | 许昌学院 | Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ |
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| CN101635315B (en) * | 2009-08-18 | 2011-03-30 | 郑直 | Chemical method for preparing three-dimensional dendritic copper selenide nano-crystalline photoelectric film material |
| CN101786650B (en) * | 2010-02-08 | 2011-11-02 | 许昌学院 | Chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature |
| CN102080263B (en) * | 2010-12-10 | 2012-11-07 | 同济大学 | Method for preparing Ag2X film |
| CN102102224B (en) * | 2011-01-07 | 2012-08-29 | 许昌学院 | Silver-copper-selenium ternary compound dendrite film material and preparation method thereof |
| CN102230224A (en) * | 2011-06-27 | 2011-11-02 | 南京大学 | Thermal evaporation synthesis method of Ag2Se nanowire and preparation method of electric measuring device |
| CN103145345B (en) * | 2013-03-20 | 2014-12-10 | 许昌学院 | Chemical method for synthesising silver selenide semiconductor photoelectric film material in situ at room temperature |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805136A (en) * | 2010-03-11 | 2010-08-18 | 许昌学院 | Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ |
| CN101805136B (en) * | 2010-03-11 | 2012-05-23 | 许昌学院 | Chemical method for in situ preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass |
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