CN101786650A - Chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature - Google Patents
Chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature Download PDFInfo
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- CN101786650A CN101786650A CN 201010111402 CN201010111402A CN101786650A CN 101786650 A CN101786650 A CN 101786650A CN 201010111402 CN201010111402 CN 201010111402 CN 201010111402 A CN201010111402 A CN 201010111402A CN 101786650 A CN101786650 A CN 101786650A
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Abstract
The invention relates to a chemical method for in situ synthesis of platy silver sulphide nano crystal photoelectric film at low temperature. The method includes that firstly sulphur powder is added into a container, and then organic solvent is added, volume of organic solvent is more than 1/2 of volume of the container, and finally base material with clean metal silver surface is placed at the bottom of the container in inclining or horizontal way, thus avoiding direct contact with sulphur powder. The base material and sulphur powder are immersed under solvent liquid level and react for 4-184 hours at the temperature of 20-60 DEG C, concentration of simple substance sulphur powder in reactant is maintained to be saturate, namely film material composed of platy silver sulphide nano crystal is prepared on the surface of the base material with clean metal silver surface by in situ, and product is washed by absolute ethyl alcohol and dried at room temperature. The method for preparing base material with clean metal silver surface includes that base material with metal silver surface is placed into absolute alcohol, is cleaned by an ultrasonic cleaner for 3min and then is soaked in DMF or absolute alcohol for spare use. The invention can be carried out at low temperature, has low energy consumption and is convenient and efficient, thus being beneficial to industrialized production.
Description
Technical field
The invention belongs to material chemistry technical field, relate in particular to the chemical process of the big area optoelectronic film that original position synthesizing flaky silver sulfide nanocrystalline is formed under a kind of low temperature.
Background technology
Silver sulfide (Ag
2S) be a kind of low energy gap width direct semiconductor, it has good chemical stability and outstanding restricted optical characteristics (optical limiting properties).Its restricted optical characteristics shows as under the nanosecond laser pulses effect and responds at wavelength 532nm place, and its numerical value is soccerballene C head and shoulders above
60With aluminium phthalocyanine muriate.Ag
2The S crystal is widely used in the manufacturing of various optics and electron device, for example photovoltaic cell, optical conductor, infrared IR detector and superionic conductor(s) etc.In nearest research, the someone has found Ag
2S also can be used as solid state memory (solid state memory) device, is used for the experimental study of electricity aspect.Ag
2S has three kinds of crystalline structure, monocline α-Ag
2S (at stable existence below 178 ℃), body-centered cubic β-Ag
2S (178～600 ℃ of stable existences), face-centered cubic γ-Ag
2S (stable existence more than 600 ℃).Wherein, α-Ag
2S is the direct N-type semiconductorN of low energy gap width, and the band-gap energy under the room temperature environment (Band gap) is approximately 1eV.
Prepare Ag at present
2S crystalline method is existing multiple, but most method has used silver salt to make reactant, has synthesized Ag under the pyritous condition
2The S crystal.The crystal that seeks out special appearance often needs to use various tensio-active agents.And the introducing of tensio-active agent is had higher requirement to the experiment post-processing operation, and has strengthened preparation cost.Wee Shong Chin seminar of NUS uses Mercaptobenzoic acid silver Ag (SCOPh) to make precursor, at first it is dissolved in trioctylphosphine phosphorus (TOP), is injected into then in hot amine (hexadecylamine) solution of 80～120 ℃ of temperature and obtains Ag through pyrolysis
2S is nanocrystalline; Li Yadong seminar of Tsing-Hua University is with Silver Nitrate (AgNO
3) the stearylamine solvent that is dissolved in heat forms silver-colored amine compound, add the sulphur powder subsequently and form Ag
2The S nucleus further makes it grow into Ag at 120 ℃
2The S nano wire; The first academician in Zhao of Fudan University east uses the room temperature liquid phase synthesizing method to synthesize Ag
2The S nanometer rod, used reactant is Silver Nitrate, thiocarbamide and NaOH, but the product that obtains not is the Ag of film morphology
2The S crystal; Zhang Xinrong seminar of Tsing-Hua University uses Silver Nitrate to do silver-colored source, and dehydrated alcohol is made solvent, and the L-halfcystine is made additive, and reaction is 10 hours under 180 ℃ solvent thermal reaction condition, has prepared Ag
2The S nanometer ball.Professor Qi Limin of Peking University uses polyacrylic acid (PAA) to prepare precursor silver oxalate (Ag as template
2C
2O
4) bundles of nanofibers, use this fibrous bundle and thioacetamide (TAA) in ethanolic soln, to react then and generate Ag
2The S bundles of nanofibers.Holland Ruitenbeek seminar uses sputtering technology to plate a layer thickness on Si (100) surface of cleaning to be 240nm, and area is 5 * 5mm
2The Ag film, use subsequently sublimed sulphur with it 1 * 10
-6Mbar, sulfuration Ag layer outside surface forms Ag under the vacuum heating conditions of 523K
2S crystal film, but its Ag
2The S surface topography does not have the crystal outward appearance of sharp outline.
Though above these methods have been prepared the Ag of various patterns
2The S crystalline material, but the use of high-temperature water by the use of thermal means has limited the size of product, and increased energy consumption; The use of Silver Nitrate, sodium hydroxide and tensio-active agent is that follow-up purification operations has been brought inconvenience, needs repetitive scrubbing ability flush away Ag
2The foreign ion of S plane of crystal absorption; The use of deleterious aminated compounds solvent, high price Ag-containing compound are done silver-colored source, and the introducing of polymer template etc., generate Ag though can control
2S crystalline pattern has also produced problems such as environmental pollution.In addition, most products are Powdered Ag
2The S crystal when being used in optoelectronic thin film material, often needs further film forming.
Professor Liu Airuo of this seminar had once gone out the Ag of tubular structure with Hydrothermal Preparation
2The brilliant film of S micron, related work are published in " printing during chemical industry " magazine, and (2008, the 22nd rolled up for the 6th phase, 29-31).Its detailed synthesis step is as described below: getting the 20mL reactor of a cleaning, get the 15mL solvent with transfer pipet and inject wherein, add 0.01g sulphur powder or sulfide, is 30mm * 8mm with tweezers gripping specification then, and thickness is that the silver strip of 1mm is put into reactor., be warming up to certain temperature and react putting into the specified location of Constant Temp. Oven after the reactor sealing with stainless steel sleeve, take out behind the constant temperature some hrs, product naturally cools to room temperature in air, and product washes after drying repeatedly through dehydrated alcohol and handles.Final product structure and pattern use x-ray powder diffraction instrument (XRD) and scanning electronic microscope (SEM) to characterize respectively.From experimental result, the SEM pattern in the article does not all obtain yardstick below 100nm and the regular Ag of outward appearance
2The S nanocrystal.Corresponding preparation condition is that the compound of sulphur such as Sulfothiorine or thiocarbamide is done the sulphur source, and dehydrated alcohol, propyl carbinol and benzene are made solvent.Write down in the article with the sulphur powder and done the sulphur source, dehydrated alcohol is made solvent, the Ag that grows at the Ag substrate surface
2S tubular crystal pattern, tube length differs, the longest 100 μ m that reach, diameter is greatly about 3～6 mu m ranges.The what is more important reaction needed is carried out under the condition of high temperature hydro-thermal.
At further Ag
2In the S crystal film material preparation research, the applicant has found a kind of above-mentioned high-temperature solvent reaction for preparation Ag that is different from
2S crystalline method at room temperature uses Ag sheet and S powder at various nontoxic organic solvent direct reaction, can go out to have the sheet Ag of regular pentagon outward appearance, the about 20nm of thickness in the surface growth of Ag sheet
2The S nano-crystal film.Easy and simple to handle, the environmental protection of whole process of preparation, energy consumption is low, uses raw materials cost cheap, and this preparation experiment good reproducibility, does not have any murder by poisoning by product.
For the semiconductor material that significant application value is arranged, no matter industrial application or laboratory study, invariably material preparation technology is had higher requirement, promptly adopt the raw material of simple technology, cheapness, cut down the consumption of energy as far as possible, synthesize environmentally safe, highly purified product is to satisfy the preparation requirement under current shortage of resources, the energy deficiency condition.
Summary of the invention
Problem to be solved by this invention is: overcome present preparation Ag
2Shortcomings such as dependent reaction container that exists in the S crystalline method and tensio-active agent, energy consumption is higher, solvent toxicity is big, product is impure, complex process.The chemical process of original position synthesizing flaky silver sulfide nanocrystalline optoelectronic film under a kind of low temperature is provided.
The present invention adopts cheap raw material, and Ag sheet, S powder and various nontoxic organic solvent can grow Ag at Ag sheet surface in situ through simple immersion process
2S nanometer sheet film, nanometer sheet thickness is about about 20nm.This method energy consumption is low, need not to use any tensio-active agent and other chemical additive again, only need and to place glass or plastic material reaction vessel at the bottom of S powder, organic solvent and the money base altogether, leave standstill more than 4 hours and to take out the seasoning of Ag sheet, promptly obtain high coverage rate, high purity, have the Ag of the perfect pattern of regular pentagon
2S nanometer sheet film, Ag
2The cohesive force of S film and Ag substrate is very strong, and general ultrasonic procedure can not make it come off, and the thickness of film can be controlled by soak time.This method also can be cut out difform metal A g sheet, be selected for use the container of differing capacities to prepare shape, the different Ag of area
2The S crystal film.
The technical scheme that the present invention takes problem to be solved is:
The large area film preparation methods that a kind of platy silver sulphide nano crystal is formed, it is characterized in that: at first the sulphur powder is joined in the container, add organic solvent N then, dinethylformamide, dehydrated alcohol, Virahol or propyl carbinol, volume of organic solvent is greater than half of vessel volume, the base material inclination or the level that will have clean metal silver surface again place container bottom, and avoid directly contacting with the sulphur powder, its base material and elemental sulfur powder with clean metal silver surface is immersed under the organic solvent liquid level, 20～60 ℃ of temperature range internal reactions 4～184 hours, the concentration of elemental sulfur powder remains on state of saturation in the reactant, promptly make the large area film material that the sheet structure silver sulfide nanocrystalline is formed in substrate material surface original position with clean metal silver surface, the product absolute ethanol washing, drying at room temperature gets final product, and wherein said container is a vial, the container of tetrafluoroethylene reactor or other anti-described organic solvent.
In the technical scheme of the present invention, described clean argent base material is meant the argent paillon foil.
In the technical scheme of the present invention, acquisition has the method for the base material of clean metal silver surface, be that the base material that will have metal silver surface places dehydrated alcohol, be soaked in N with the ultrasonic cleaner cleaning after 3 minutes, dinethylformamide (DMF) N, stand-by in dinethylformamide, dehydrated alcohol, Virahol or the propyl carbinol.
Advantage of the present invention:
1, at low temperatures, with simple organic solvent as reaction medium, by the step optoelectronic film directly be made up of platy silver sulphide nano crystal in the metal silver surface in-situ preparing of chemical reaction, the silver sulfide product purity height of generation can obtain the regular pentagon nano-sheet crystal of symmetrical configuration.
2, under ambient temperature, can react, the reaction conditions gentleness, need not to heat, traditional energy drives reactions such as illumination, microwave radiation carry out, energy consumption low (room temperature reaction does not have energy consumption), easy to operate, reaction is quick, only need two kinds of reactants are immersed in the organic solvent, the product impure phenomenon that can avoid other wet chemistry prepared in reaction to be caused, and the shape of the silver sulfide film that generates, area, thickness etc. all can by the kind of reactant A g sheet, organic solvent, and reaction times etc. control.
3, the present invention directly is immersed in two kinds of reactants in the organic solvent, does not need special reaction vessel, and can be on metal silver surface direct film forming, thereby overcome the shortcoming of method complex process such as gel method, vapor deposition method, spraying pyrolytic decomposition.
4, need not to use bigger solvent of toxicity such as triphenylphosphine, hydrazine hydrate, quadrol, octadecylene etc., belong to environmentally friendly reaction.Simultaneously do not need to use any tensio-active agent such as cetyl trimethylammonium bromide (CTAB) etc., can large-area preparation, be convenient to suitability for industrialized production and technology popularization.
5, low temperature test good reproducibility, film surface is very evenly smooth, has solved the uneven problem of additive method crystal film.
Description of drawings
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 1, embodiment 1 preparation
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 2, embodiment 2 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 3, embodiment 3 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 4, embodiment 4 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 5, embodiment 5 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 6, embodiment 6 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 7, embodiment 7 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 8, embodiment 8 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Fig. 9, embodiment 9 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 10, embodiment 10 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 11, embodiment 11 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 12, embodiment 12 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 13, embodiment 13 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 14, embodiment 14 preparations
The scanning electron photomicrograph of the silver sulfide nanocrystalline thin-film material of Figure 15, embodiment 15 preparations
The XRD figure of product spectrum among Figure 16, the embodiment 1 (* of sign number expression silver)
The EDX collection of illustrative plates of product among Figure 17, the embodiment 1
Embodiment
Further specify the large area film preparation methods that this sheet silver sulfide nanocrystalline is formed below by embodiment.
1, preparation work: analytical pure silver strip (long 2cm, wide 0.3cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in the dehydrated alcohol stand-by after 3 minutes with the ultrasonic cleaner cleaning; (volume 20ml) uses tap water, distilled water, absolute ethanol washing successively with the tetrafluoroethylene reactor, and dry back is stand-by;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml dehydrated alcohol, the tetrafluoroethylene reactor is put in the argent paillon foil inclination of handling, avoid directly contacting with the sulphur powder! The tetrafluoroethylene reactor is placed stable place, 20 ℃ of reactions 64 hours;
3, aftertreatment: after reaction finished, surperficial no ethanol was residual gets final product be dried to product after the dehydrated alcohol wash products 3 times under room temperature, obtains the silver sulfide film sample, carefully changes over to then in the sample bottle, preserves in lucifuge, exsiccant environment.Product colour is a black, and the microtexture under scanning electronic microscope is the flaky nanocrystalline (the about 20nm of thickness) of plane regular pentagon.Scanning electron photomicrograph is seen Fig. 1.X-ray powder diffraction (XRD) collection of illustrative plates of product is seen Figure 16, the * of sign number expression silver.The energy spectrum analysis of product (EDX) collection of illustrative plates is seen Figure 17.
1, preparation work: with embodiment 1.
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml dehydrated alcohol, the tetrafluoroethylene reactor is put in the argent paillon foil inclination of handling, avoid directly contacting with the sulphur powder! The tetrafluoroethylene reactor is placed stable place, 20 ℃ of reactions 184 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is the flaky nanocrystalline of plane regular pentagon.Scanning electron photomicrograph is seen Fig. 2.
1, preparation work: analytical pure silver strip (long 1cm, wide 0.3cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in the dehydrated alcohol stand-by after 3 minutes with the ultrasonic cleaner cleaning; (volume 20ml) uses tap water, distilled water, absolute ethanol washing successively with the tetrafluoroethylene reactor, and dry back is stand-by;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml dehydrated alcohol, the argent paillon foil level of handling is put into bottom the reactor, avoid directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 4 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 3.
1, preparation work: with embodiment 3;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml dehydrated alcohol, the argent paillon foil level of handling is put into bottom the reactor, avoid directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 8 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 4.
1, preparation work: with embodiment 3;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml dehydrated alcohol, the argent paillon foil level of handling is put into bottom the reactor, avoid directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 24 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 5.
1, preparation work: analytical pure silver strip (long 1cm, wide 0.3cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in N after 3 minutes with the ultrasonic cleaner cleaning, stand-by in the dinethylformamide; (volume 8ml) uses tap water, distilled water, absolute ethanol washing successively with vial, and dry back is stand-by;
2, reactions steps: take by weighing 0.01g sulphur powder in vial (volume 8ml), fill 7mlN, dinethylformamide is put into the vial bottom with the argent paillon foil level of handling, and avoids directly contacting with the sulphur powder! Vial is placed stable place, 20 ℃ of reactions 8 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 6.
Embodiment 7
1, preparation work: with embodiment 6;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 8ml) that step 1 handled, fill 7mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the vial, avoids directly contacting with the sulphur powder! Vial is placed stable place, 20 ℃ of reactions 12 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 7.
Embodiment 8
1, preparation work: with embodiment 6;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 8ml) that step 1 handled, fill 7mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the vial, avoids directly contacting with the sulphur powder! Vial is placed stable place, 20 ℃ of reactions 24 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 8.
Embodiment 9
1, preparation work: with embodiment 6;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 8ml) that step 1 handled, fill 7mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the vial, avoids directly contacting with the sulphur powder! Vial is placed stable place, 20 ℃ of reactions 35 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Fig. 9.
1, preparation work: with embodiment 6;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 8ml) that step 1 handled, fill 7mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the vial, avoids directly contacting with the sulphur powder! Vial is placed stable place, 25 ℃ of reactions 24 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 10.
1, preparation work: analytical pure silver strip (long 1cm, wide 0.3cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in N after 3 minutes with the ultrasonic cleaner cleaning, stand-by in the dinethylformamide; (volume 20ml) uses tap water, distilled water, absolute ethanol washing successively with the tetrafluoroethylene reactor, and dry back is stand-by;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill 15mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the reactor, avoids directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 4 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 11.
Embodiment 12
1, preparation work: with embodiment 11;
2, reactions steps: take by weighing 0.01g sulphur powder in tetrafluoroethylene reactor (volume 20ml), fill 15mlN, dinethylformamide is put into the reactor bottom with the argent paillon foil level of handling, and avoids directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 8 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 12.
Embodiment 13
1, preparation work: with embodiment 11;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill 15mlN, dinethylformamide is put into the argent paillon foil level of handling bottom the reactor, avoids directly contacting with the sulphur powder! Reactor is placed stable place, 60 ℃ of reactions 24 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 13.
1, preparation work: analytical pure silver strip (long 3.5cm, wide 0.5cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in the Virahol stand-by after 3 minutes with the ultrasonic cleaner cleaning; (volume 20ml) uses tap water, distilled water, absolute ethanol washing successively with the tetrafluoroethylene reactor, and dry back is stand-by;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml Virahol, the argent paillon foil inclination of handling is put into reactor inside, avoid directly contacting with the sulphur powder! Reactor is placed stable place, 20 ℃ of reactions 64 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 14.
Embodiment 15
1, preparation work: analytical pure silver strip (long 3.5cm, wide 0.5cm, thick 0.2mm) flattening is placed in the dehydrated alcohol, is soaked in the propyl carbinol stand-by after 3 minutes with the ultrasonic cleaner cleaning; (volume 20ml) uses tap water, distilled water, absolute ethanol washing successively with the tetrafluoroethylene reactor, and dry back is stand-by;
2, a reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml) that step 1 handled, fill the 15ml propyl carbinol, the argent paillon foil inclination of handling is put into reactor inside, avoid directly contacting with the sulphur powder! Reactor is placed stable place, 20 ℃ of reactions 64 hours;
3, aftertreatment: with embodiment 1.Product colour is a black, and the microtexture under scanning electronic microscope is a flaky nanocrystalline.Scanning electron photomicrograph is seen Figure 15.
The present invention uses simply solvent N, dinethylformamide, dehydrated alcohol, Virahol or propyl carbinol are as reaction medium, directly adopt elemental sulfur and argent substrate to go out the semiconductor film material that large-area platy silver sulphide nano crystal is formed through the single step reaction in-situ preparing at low temperatures, energy consumption of reaction is low or do not have an energy consumption.Of no use to any additive and tensio-active agent, belong to environmentally friendly reaction.Do not need subsequent purification step, film surface is even, smooth.Easy to operate, reaction is quick, is convenient to suitability for industrialized production and technology popularization.Because less energy consumption and the simple aftertreatment of product meeting reduce cost greatly.
Claims (3)
1. the large area film preparation methods formed of a platy silver sulphide nano crystal, it is characterized in that: at first the sulphur powder is joined in the container, add organic solvent N then, dinethylformamide, dehydrated alcohol, Virahol or propyl carbinol, volume of organic solvent is greater than half of vessel volume, the base material inclination or the level that will have clean metal silver surface again place container bottom, and avoid directly contacting with the sulphur powder, it has the base material of clean metal silver surface, the elemental sulfur powder, be immersed under the organic solvent liquid level, 20～60 ℃ of temperature range internal reactions 4～184 hours, the concentration of elemental sulfur powder remains on state of saturation in the reactant, promptly make the large area film material that the sheet structure silver sulfide nanocrystalline is formed in substrate material surface original position with clean metal silver surface, the product absolute ethanol washing, drying at room temperature gets final product, and wherein said container is a vial, the container of tetrafluoroethylene reactor or other anti-described organic solvent.
2. the large area film preparation methods that platy silver sulphide nano crystal as claimed in claim 1 is formed, it is characterized in that: described clean argent base material is meant the argent paillon foil.
3. the large area film preparation methods that platy silver sulphide nano crystal as claimed in claim 1 is formed, it is characterized in that: acquisition has the method for the base material of clean metal silver surface, be that the base material that will have metal silver surface places dehydrated alcohol, be soaked in N with the ultrasonic cleaner cleaning after 3 minutes, stand-by in dinethylformamide, dehydrated alcohol, Virahol or the propyl carbinol.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1260118C (en) * | 2004-09-24 | 2006-06-21 | 武汉大学 | Preparation for metal sulfide |
| CN100545081C (en) * | 2007-07-12 | 2009-09-30 | 许昌学院 | Dendritic silver selenide nano crystal thin film material and preparation method |
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|---|---|---|---|---|
| CN102509769A (en) * | 2011-10-28 | 2012-06-20 | 许昌学院 | Ag2S flaky nanocrystal array and P3HT hybridized film photoelectric converting apparatus prepared based on low temperature |
| CN102509769B (en) * | 2011-10-28 | 2013-12-04 | 许昌学院 | Ag2S flaky nanocrystal array and P3HT hybridized film photoelectric converting apparatus prepared based on low temperature |
| CN105293561A (en) * | 2015-11-05 | 2016-02-03 | 南昌航空大学 | Method for preparing needle-shaped Ag2S microparticles through organic molten salt method |
| CN107233898A (en) * | 2017-07-10 | 2017-10-10 | 苏州科技大学 | Preconcentration with activated carbon collaboration full spectrum light catalysis material and preparation method thereof |
| WO2019153335A1 (en) * | 2018-02-06 | 2019-08-15 | 中国科学院上海硅酸盐研究所 | Plastic semiconductor material and preparation method thereof |
| JP2021511279A (en) * | 2018-02-06 | 2021-05-06 | 中国科学院上海硅酸塩研究所 | Plastic semiconductor materials and their manufacturing methods |
| US11136692B2 (en) | 2018-02-06 | 2021-10-05 | Shanghai Institute Of Ceramics, Chinese Academy Of Sciences | Plastic semiconductor material and preparation method thereof |
| JP7028985B2 (en) | 2018-02-06 | 2022-03-02 | 中国科学院上海硅酸塩研究所 | Plastic semiconductor materials and their manufacturing methods |
| CN112899646A (en) * | 2019-11-19 | 2021-06-04 | 中国科学院微电子研究所 | Ag preparation based on silver acetylacetonate2Method for preparing S film |
| CN111533462A (en) * | 2020-04-06 | 2020-08-14 | 许昌学院 | Chemical method for rapidly synthesizing silver sulfide film at normal temperature |
| CN112701188A (en) * | 2020-12-29 | 2021-04-23 | 杭州电子科技大学 | Near-infrared photoelectric detector and preparation method thereof |
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