CN101792173B - Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature - Google Patents
Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature Download PDFInfo
- Publication number
- CN101792173B CN101792173B CN2010101114035A CN201010111403A CN101792173B CN 101792173 B CN101792173 B CN 101792173B CN 2010101114035 A CN2010101114035 A CN 2010101114035A CN 201010111403 A CN201010111403 A CN 201010111403A CN 101792173 B CN101792173 B CN 101792173B
- Authority
- CN
- China
- Prior art keywords
- copper
- nanocrystalline
- film
- container
- sulphur powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention provides a chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at a low temperature. The method comprises the following steps: firstly adding sulfur powder in a container, secondly adding organic solvent N,N-dimethylformamide or absolute alcohol, wherein the volume of organic solvent is more than a half of the capacity of the container; standing at 0-60 DEG C for 1h to ensure that the sulfur powder dissolved in organic solvent is saturated, horizontally placing substrate material with a new and clean metal copper surface on the bottom of the container to avoid directly contacting with sulfur powder, reacting at 0-60 DEG C for 5-24h, cleaning the product with absolute alcohol, drying at room temperature to in-situ prepare the big area film material composed of flaky CuxSy nanocrystalline on the metal copper surface of the substrate material, wherein x:y=1-2. The method of the invention adopts low temperature, has low energy consumption, is simple, green and environmentally friendly and particularly applicable to large-area industrial production, and does not use any template, add any surfactant and perform complicated post-processing operations such as purification.
Description
Technical field:
The invention belongs to material chemistry technical field, relate in particular to big area synthesizing flaky Cu under a kind of low temperature
xS
yThe chemical process of x: y=1～2 nano-crystalline photoelectric film materials.
Background technology:
Sulfide (the Cu of copper
xS
yX: y=1～2) be a kind of important binary compound, and this compound is known by people because it exists many non-stoichiometric combinations and heterogeneous admixture.The sulfide that has 5 kinds of stable at ambient temperature copper now at least, rich sulphur is mutually: covellite (CuS); Copper-rich phase is: anilite (Cu
1.75S), alpha chalcocite (Cu
1.8S), djurleite (Cu
1.95S) and copper glance (Cu
2S).The sulfide of the copper that synthesizes now comprises CuS more than 21 kinds, Cu
1.96S, Cu
7S
4, Cu
9S
5, Cu
2S or the like.At present, such thin-film material is as a kind of important photoelectric semiconductor material, because of potential application, be subjected to material supply section scholar's extensive concern in fields such as solar cell material, optical-thermal conversion material, electrode materials, microwave masking material, lithium rechargeable battery cathode material and other chemical sensitisation modulator material.
In recent years, the synthetic method of the sulfide of copper has had many reports, and these methods comprise: microwave assisting method, solvent-thermal method, sonochemical method, microemulsion method and precursor method etc.Above method often will be carried out under relatively fiercer conditioned disjunction comparatively high temps, consumes a large amount of energy simultaneously; What have will add additive such as tensio-active agent or utilize complicated solvent system, have in addition to utilize the bigger organic solvent of toxicity, unfriendly to environment, also brought certain trouble for simultaneously the aftertreatment of product, be unfavorable for industrialized production.Report in the recent period; Lanzhou Physical and Chemical Inst. of the Chinese Academy of Sciences beautiful grade of Lu Yong utilizes the method for chemical bath to synthesize the cuprous sulfide nano-crystal film; but this method still needs heat treated in the solution-treated process, particularly at last need be to deposit film 300 ℃ of sintering processes under nitrogen protection.2006, Zhaodong Nan etc. delivers the academic paper that is entitled as " Formation of various morphologies of coppersulfides by a solvothermal method " on Journal of Crystal Growth, with analytically pure anhydrous cupric sulfate, thiocarbamide is reactant, with ethylene glycol is solvent, utilizes solvent-thermal method to synthesize Cu by mol ratio and the temperature condition that changes raw material
7S
4, Cu
31S
16, Cu
1.8S, Cu
2The sulfide of multiple copper such as S.In June, 2008, Peng Meng etc. deliver on " Hubei University's journal " and are entitled as " nanometer Cu
2The preparation and the optics catalytic property of S flower ", adopting this method synthetic nanometer cuprous sulfide is pulverulence, and entire reaction need be carried out under 180 ℃ high-temperature solvent heat condition.2002, Inorganic Chemistry Communications delivered and is entitled as " Aqueous ammonia route to Cu
1.8S with triangular and rod-like shapes " academic paper, be solvent with ammoniacal liquor, with CuCl
22H
2O and sulphur powder are reactant, utilize solvent-thermal method to react 10 hours under 160 ℃ of conditions, obtain Cu
1.8S.
2007, S.Gorai etc. deliver the academic paper that is entitled as " Morphological control insolvothermal synthesis of copper sulphides on copper foil " at Materials Research Bulletin, with water, ethanol, quadrol etc. is that solvent, Copper Foil and sulphur powder are that reactant is in the tetrafluoroethylene reactor, reacted 12 hours under 75% compactedness, 130 ℃ of conditions, prepared Cu respectively
9S
5And Cu
2The S crystal.Materials Letters delivered and is entitled as " Controllablehydrothermal synthesis of Cu in 2009
2S nanowires on the copper substrate " academic paper, adopt the synthetic cuprous sulfide nano-crystal film of solvent-thermal method.Concrete synthetic schemes is as described below: (thickness: 0.2mm, long * is wide: 2*2cm with copper sheet
2), lmmol sulphur powder, 1ml hydrazine hydrate and 1mmol CTAB (cetyl trimethylammonium bromide) join in the tetrafluoroethylene reactor, add 25ml distilled water then, reactor is kept in 180 ℃ environment after 12 hours and is naturally cooled to room temperature, and the thin-film material that obtains characterizes after with the dehydrated alcohol cleaning-drying.More than these methods mostly in relatively-high temperature highly compressed solvent thermal or hydrothermal reaction kettle, finish, all to consume certain energy, also will depend on certain tensio-active agent, even deleterious hydrazine hydrate solution, and the sulfide for preparing large-area copper to be subjected to the restriction of reaction unit.
Therefore, seek the method for a kind of low temperature, less energy-consumption, simple and environmental protection, use low cost raw material big area under avirulent condition directly to prepare Cu
xS
yX: y=1～2 thin-film materials remain the problem that need research and solve.
Summary of the invention:
Problem to be solved by this invention is: overcome present preparation Cu
xS
yDependent reaction container and the tensio-active agent that exists in x: y=1～2 crystalline methods, shortcomings such as energy consumption is higher, solvent toxicity is big, product is impure, complex process.A kind of low temperature less energy-consumption, environmental protection be provided, be suitable for the big area industrial production, without any need for template, do not need to add any tensio-active agent, needn't can make highly purified Cu through loaded down with trivial details post-processing operation such as removal of impurities
xS
yThe method of x: y=1～2 flaky nanocrystalline optoelectronic thin film materials.In addition, the present invention by a step cryochemistry reaction directly in the substrate of metal, semi-conductor etc. growth in situ go out big area sheet Cu
xS
yX: y=1～2 nano-crystal films is so that wide industrial is used.
The technical scheme that the present invention takes the problem that will solve is:
A kind of by sheet Cu
xS
yThe low temperature preparation method of the thin-film material of x: y=1～2 nanocrystalline compositions, it is characterized in that: at first the sulphur powder is joined in the container, add organic solvent N then, dinethylformamide (DMF) or dehydrated alcohol, constant temperature was placed 1 hour in 0～60 ℃ of temperature range, dissolved sulphur powder is reached capacity in organic solvent, the base material level that will have new and clean copper surface again places container bottom and avoids directly contacting with the sulphur powder, under 0～60 ℃ of temperature condition, reacted 5～24 hours, the product absolute ethanol washing, in drying at room temperature, promptly the surface in situ at the base material metallic copper makes sheet structure Cu
xS
yThe large area film material of x: y=1～2 nanocrystalline compositions; Described container is the container of glass beaker, tetrafluoroethylene reactor or other anti-described organic solvent.
In the technical scheme of the present invention, described container is a vial, the container of tetrafluoroethylene reactor or other anti-described organic solvent.
In the technical scheme of the present invention, described base material with new and clean copper surface is meant the metallic copper paillon foil, and the ITO conductive glass sheet of layer of metal copper has been plated on the surface.
In the technical scheme of the present invention, plate the method for layer of metal copper film for electroplating or ion sputtering at ITO conductive glass or other material surface.
In the technical scheme of the present invention, acquisition has the method for the base material of new and clean copper surface: to metal copper foil is to put into the beaker that fills dilute hydrochloric acid and ethanol solution after the flattening of metallic copper paillon foil, be soaked in N with the ultrasonic cleaner cleaning after 3 minutes, stand-by in dinethylformamide or the dehydrated alcohol, described dilute hydrochloric acid is concentrated hydrochloric acid and 1: 20 acid of deionized water volume ratio; To the ITO conductive glass sheet that is coated with the metallic copper film is that the ITO conductive glass sheet that will plate the metallic copper film is soaked in N, stand-by in the dinethylformamide.
Advantage of the present invention:
1, can make by sheet Cu
xS
yThe large area film material of x: y=1～2 nanocrystalline compositions, temperature of reaction is low, and energy consumption is lower or do not have energy consumption, and is easy to operate, and reaction is quick, the product impure phenomenon that can also avoid other wet chemistry prepared in reaction to be caused.The Cu that forms by flaky nanocrystalline
xS
yX: y=1～2 films, wherein the ratio of Cu and S can be controlled by parameters such as temperature of reaction, solvent, reaction times.
2, do not need special reaction vessel, and can be on various base materials with copper surface direct film forming, thereby overcome the shortcoming of method complex process such as gel method, vapor deposition method, spraying pyrolytic decomposition.
3, need not to use bigger solvent of toxicity such as triphenylphosphine, hydrazine hydrate, quadrol, octadecylene etc., belong to environmentally friendly reaction, do not need to use simultaneously 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.
4, low temperature test good reproducibility, flaky nanocrystalline pattern homogeneous, perfection, film surface is very evenly smooth, has solved the uneven problem of additive method crystal film.
Description of drawings
The Cu of Fig. 1-1, embodiment 1 preparation
2The scanning electron photomicrograph of S nano crystal thin film material
The Cu of Fig. 1-2, embodiment 1 preparation
2The XRD figure spectrum of S nano crystal thin film material
The Cu of Fig. 2-1, embodiment 2 preparations
2The scanning electron photomicrograph of S nano crystal thin film material
The Cu of Fig. 2-2, embodiment 2 preparations
2The XRD figure spectrum of S nano crystal thin film material
The Cu of Fig. 3-1, embodiment 3 preparations
8S
9And Cu
2The scanning electron photomicrograph of S two-phase mixed nano-crystal thin-film material
The Cu of Fig. 3-2, embodiment 3 preparations
8S
9And Cu
2The XRD figure spectrum of S two-phase mixed nano-crystal thin-film material
The Cu of Fig. 4-1, embodiment 4 preparations
8S
9And Cu
2The scanning electron photomicrograph of S two-phase mixed nano-crystal thin-film material
The Cu of Fig. 4-2, embodiment 4 preparations
8S
9And Cu
2The XRD figure spectrum of S two-phase mixed nano-crystal thin-film material
The Cu of Fig. 5-1, embodiment 5 preparations
39S
28And Cu
2The scanning electron photomicrograph of S two-phase mixed crystal thin film material
The Cu of Fig. 5-2, embodiment 5 preparations
39S
28And Cu
2The XRD figure spectrum of S two-phase mixed crystal thin film material
The scanning electron photomicrograph of the CuS nano crystal thin film material of Fig. 6-1, embodiment 6 preparations
The XRD figure spectrum of the CuS nano crystal thin film material of Fig. 6-2, embodiment 6 preparations
The scanning electron photomicrograph of the CuS nano crystal thin film material of Fig. 7-1, embodiment 7 preparations
The XRD figure spectrum of the CuS nano crystal thin film material of Fig. 7-2, embodiment 7 preparations
The scanning electron photomicrograph of the CuS nano crystal thin film material of Fig. 8-1, embodiment 8 preparations
The XRD figure spectrum of the CuS nano crystal thin film material of Fig. 8-2, embodiment 8 preparations
The scanning electron photomicrograph of the CuS nano crystal thin film material of Fig. 9-1, embodiment 9 preparations
The XRD figure spectrum of the CuS nano crystal thin film material of Fig. 9-2, embodiment 9 preparations
The scanning electron photomicrograph of the CuS nano crystal thin film material of Figure 10-1, embodiment 10 preparations
The XRD figure spectrum of the CuS nano crystal thin film material of Figure 10-2, embodiment 10 preparations
The Cu of Figure 11-1, embodiment 11 preparations
7.2S
4The scanning electron photomicrograph of nano crystal thin film material
The Cu of Figure 11-2, embodiment 11 preparations
7.2S
4The XRD figure spectrum of nano crystal thin film material
Among the figure ▲ and the diffraction peak of the CuS tabular crystal film that representative generates, corresponding PDF card number: 6-464; The Cu that the ★ representative generates among the figure
2The diffraction peak of S tabular crystal film, corresponding PDF card number: 12-227; The Cu that the ☆ representative generates among the figure
2The diffraction peak of S tabular crystal film, corresponding PDF card number: 46-1195; Among the figure ◆ the Cu that representative generates
39S
28The diffraction peak of tabular crystal film, corresponding PDF card number: 36-380; Among the figure ● the Cu that representative generates
8S
9The diffraction peak of tabular crystal film, corresponding PDF card number: 36-379; Among the figure
The Cu that representative generates
7.2S
4The diffraction peak of tabular crystal film, corresponding PDF card number: 72-1966.
Other diffraction peak is from unreacted metal copper or substrate I TO.
Embodiment
Further specify sheet Cu of the present invention below by embodiment
xS
yThe large area film preparation methods of x: y=1～2 nanocrystalline compositions.
Embodiment 1
1, preparation work: will put in the beaker that fills dilute hydrochloric acid (concentrated hydrochloric acid and deionized water, volume ratio 1: 20) and ethanol solution after the flattening of analytical pure metallic copper paillon foil, be soaked in N after 3 minutes with the ultrasonic cleaner cleaning, stand-by in the N-2 methylformamide; (volume 10ml) 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 and be put in step 1 and get ready in the vial (volume 10ml), fill N then, dinethylformamide 8ml, constant temperature is 1 hour in ice-water bath, then the sulphur powder is inclined to vial bottom one side, the metallic copper paillon foil level of handling through step 1 is put into vial, avoid directly contacting with the sulphur powder, place ice-water bath in the reaction of stable place vial, 0 ℃ of reaction 18 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 Cu
2The S film sample carefully changes in the sample bottle then, preserves in lucifuge, exsiccant environment.Product colour is a grey black, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 1-1, and the XRD figure spectrum is seen Fig. 1-2.
1, preparation work: with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 10ml) that step 1 gets ready, fill N then, dinethylformamide 8ml, constant temperature is 1 hour in ice-water bath, then the sulphur powder is inclined to vial bottom one side, the metallic copper paillon foil level of handling through step 1 is put into vial, avoid directly contacting with the sulphur powder, place ice-water bath in the reaction of stable place vial, 0 ℃ of reaction 24 hours;
3, aftertreatment:, obtain Cu with embodiment 1
2The S film sample.Product colour is a grey black, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 2-1, and the XRD figure spectrum is seen Fig. 2-2.
1, preparation work: with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the vial (volume 10ml) that step 1 gets ready, fill N then, dinethylformamide 8ml, under 20 ℃ of conditions, placed 1 hour, then the sulphur powder is inclined to vial bottom one side, will put into vial, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, vial is placed the reaction of stable place, 20 ℃ of reactions 8 hours;
3, aftertreatment:, obtain Cu with embodiment 1
8S
9And Cu
2S two-phase mixed nano-crystal film sample.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 3-1, and the XRD figure spectrum is seen Fig. 3-2.
Embodiment 4
1, preparation work: with embodiment 1;
2, reactions steps:: take by weighing 0.01g sulphur powder and be put in the vial (volume 10ml) that step 1 gets ready, fill N then, dinethylformamide 8ml, under 20 ℃ of conditions, placed 1 hour, then the sulphur powder is inclined to vial bottom one side, will put into vial, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, vial is placed the reaction of stable place, 20 ℃ of reactions 24 hours;
3, aftertreatment:, obtain Cu with embodiment 1
8S
9And Cu
2S two-phase mixed nano-crystal film sample.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 4-1, and the XRD figure spectrum is seen Fig. 4-2.
1, preparation work: analytical pure metallic copper paillon foil put into fill dilute hydrochloric acid (concentrated hydrochloric acid and deionized water, volume ratio 1: 20) and in the beaker of ethanol solution, clean in being soaked in after 3 minutes stand-by with ultrasonic cleaner, (volume 10ml) 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 and be put in step 1 and get ready in the vial (volume 10ml), fill dehydrated alcohol 8ml then, under 20 ℃ of conditions, placed 1 hour, then the sulphur powder is inclined to vial bottom one side, to put into vial through the metallic copper paillon foil level that step 1 was handled, avoid directly contacting, vial is placed the reaction of stable place, 20 ℃ of reactions 8 hours with the sulphur powder;
3, aftertreatment:, obtain Cu with embodiment 1
39S
28And Cu
2S two-phase mixed crystal thin film sample.Product colour is black-and-blue.Scanning electron photomicrograph is seen Fig. 5-1, and the XRD figure spectrum is seen Fig. 5-2.
Embodiment 6
1, preparation work: the cleaning of metallic copper paillon foil is with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml), fill N then, dinethylformamide 15ml, constant temperature is 1 hour under 60 ℃ of conditions, then the sulphur powder is inclined to reactor bottom one side, will put into reactor, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, reactor is placed the reaction of stable place, 60 ℃ of reactions 5 hours;
3, aftertreatment:, obtain the CuS film sample with embodiment 1.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 6-1, and the XRD collection of illustrative plates is seen Fig. 6-2.
Embodiment 7
1, preparation work: the cleaning of metallic copper paillon foil is with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml), fill N then, dinethylformamide 15ml, constant temperature is 1 hour under 60 ℃ of conditions, then the sulphur powder is inclined to reactor bottom one side, will put into reactor, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, reactor is placed the reaction of stable place, 60 ℃ of reactions 8 hours;
3, aftertreatment:, obtain the CuS film sample with embodiment 1.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 7-1, and the XRD figure spectrum is seen Fig. 7-2.
1, preparation work: the cleaning of metallic copper paillon foil is with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml), fill N then, dinethylformamide 15ml, constant temperature is 1 hour under 60 ℃ of conditions, then the sulphur powder is inclined to reactor bottom one side, will put into reactor, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, reactor is placed the reaction of stable place, 60 ℃ of reactions 12 hours;
3, aftertreatment:, obtain the CuS film sample with embodiment 1.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 8-1, and the XRD figure spectrum is seen Fig. 8-2.
Embodiment 9
1, preparation work: the cleaning of metallic copper paillon foil is with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml), fill N then, dinethylformamide 15ml, constant temperature is 1 hour under 60 ℃ of conditions, then the sulphur powder is inclined to reactor bottom one side, will put into reactor, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, reactor is placed the reaction of stable place, 60 ℃ of reactions 18 hours;
3, aftertreatment:, obtain the CuS film sample with embodiment 1.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Fig. 9-1, and the XRD figure spectrum is seen Fig. 9-2.
1, preparation work: the cleaning of metallic copper paillon foil is with embodiment 1;
2, reactions steps: take by weighing 0.01g sulphur powder and be put in the tetrafluoroethylene reactor (volume 20ml), fill N then, dinethylformamide 15ml, constant temperature is 1 hour under 60 ℃ of conditions, then the sulphur powder is inclined to reactor bottom one side, will put into reactor, avoid directly contacting with the sulphur powder through the metallic copper paillon foil level that step 1 was handled, reactor is placed the reaction of stable place, 60 ℃ of reactions 24 hours;
3, aftertreatment:, obtain the CuS film sample with embodiment 1.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is even, the smooth big area flaky nanocrystalline in surface.Scanning electron photomicrograph is seen Figure 10-1, and the XRD figure spectrum is seen Figure 10-2.
1, preparation work: with electric plating method plated metal copper film on conductive glass, be soaked in N with electroplating good copper substrate, stand-by in the dinethylformamide; (volume 10ml) 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 and be put in step 1 and get ready in the vial (volume 10ml), fill 8mlN then, dinethylformamide, under 20 ℃ of conditions, placed 1 hour and the sulphur powder is inclined to vial bottom one side, finish being placed in the ice-water bath constant temperature 30 minutes, the conductive glass sheet level that is coated with the metal copper film is put into vial, avoid directly contacting with the sulphur powder, place ice-water bath in the reaction of stable place vial, 0 ℃ of reaction 24 hours;
3, aftertreatment:, obtain Cu with embodiment 1
7.2S
4Film sample.Product colour is black-and-blue, and the microtexture under scanning electronic microscope is the flaky nanocrystalline that is coated on the elemental copper particle surface.Scanning electron photomicrograph is seen Figure 11-1, and the XRD figure spectrum is seen Figure 11-2.
The present invention uses simply solvent N, dinethylformamide or dehydrated alcohol be as reaction medium, directly adopts elemental sulfur and metallic copper substrate (metal copper foil, be coated with the conductive glass of metal copper film etc.) to go out large-area sheet Cu through the single step reaction in-situ preparing at low temperatures
xS
yX: y=1～2 nano-crystalline photoelectric film materials.Of no use to any additive and tensio-active agent, belong to environmentally friendly reaction.Do not need subsequent purification step, and the perfection of film crystal formation, film surface is even, smooth.Easy to operate, reaction is quick, and energy consumption is low or do not have energy consumption, 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 (2)
1. one kind by sheet Cu
xS
yThe low temperature preparation method of the thin-film material of x: y=1～2 nanocrystalline compositions, it is characterized in that: at first the sulphur powder is joined in the container, add organic solvent N then, dinethylformamide or dehydrated alcohol, constant temperature was placed 1 hour in 0～60 ℃ of temperature range, dissolved sulphur powder is reached capacity in organic solvent, the base material level that will have new and clean copper surface again places container bottom and avoids directly contacting with the sulphur powder, under 0～60 ℃ of temperature condition, reacted 5～24 hours, the product absolute ethanol washing, in drying at room temperature, promptly the surface in situ at the base material metallic copper makes sheet structure Cu
xS
yThe thin-film material of x: y=1～2 nanocrystalline compositions; Described container is the container of glass beaker, tetrafluoroethylene reactor or other anti-described organic solvent;
Wherein, described base material with new and clean copper surface is meant the metallic copper paillon foil, and the ITO conductive glass sheet of layer of metal copper has been plated on the surface;
Acquisition has the method for the base material of new and clean copper surface: to metal copper foil is to put into the beaker that fills dilute hydrochloric acid and ethanol solution after the flattening of metallic copper paillon foil, be soaked in N with the ultrasonic cleaner cleaning after 3 minutes, stand-by in dinethylformamide or the dehydrated alcohol; To the ITO conductive glass sheet that is coated with the metallic copper film is that the ITO conductive glass sheet that will plate the metallic copper film is soaked in N, and stand-by in the dinethylformamide, described dilute hydrochloric acid is concentrated hydrochloric acid and 1: 20 acid of deionized water volume ratio.
2. sheet Cu as claimed in claim 1
xS
yThe low temperature preparation method of the thin-film material of x: y=1～2 nanocrystalline compositions is characterized in that: the method that plates layer of metal copper film on ITO conductive glass sheet surface is for electroplating or ion sputtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101114035A CN101792173B (en) | 2010-02-08 | 2010-02-08 | Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101114035A CN101792173B (en) | 2010-02-08 | 2010-02-08 | Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101792173A CN101792173A (en) | 2010-08-04 |
| CN101792173B true CN101792173B (en) | 2011-12-14 |
Family
ID=42585131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101114035A Expired - Fee Related CN101792173B (en) | 2010-02-08 | 2010-02-08 | Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101792173B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033481A (en) * | 2018-02-05 | 2018-05-15 | 重庆交通大学 | The preparation method of orienting stephanoporate copper sulfide nano material |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102133534A (en) * | 2011-03-11 | 2011-07-27 | 许昌学院 | Preparation method and application of CuS catalyst with three-dimensional framework structure |
| CN102502776B (en) * | 2011-11-23 | 2013-12-25 | 陕西科技大学 | Method for preparing Cu1.8S nanowire by microwave-hydrothermal method |
| CN102515559B (en) * | 2011-11-23 | 2013-08-14 | 陕西科技大学 | Method for preparing copper sulfide film with microwave hydrothermal assisted sol-gel method |
| CN103117173B (en) * | 2013-03-11 | 2016-02-10 | 武汉大学 | Can two-sided enter the quantum dot sensitized solar cell and preparation method thereof of light |
| CN103449502B (en) * | 2013-09-03 | 2015-01-21 | 许昌学院 | Cu7.2S4+x superlattice nano wire material and preparation method thereof |
| CN103482678B (en) * | 2013-09-10 | 2015-01-21 | 东华大学 | Method for preparing Cu7.2S4 nanocrystals with high photothermal performance |
| CN103601232B (en) * | 2013-09-18 | 2015-04-15 | 重庆大学 | Preparation method of KCu7S4 nano wire, and capacitor |
| CN104952626B (en) * | 2015-05-19 | 2017-12-01 | 温州大学 | It is a kind of nanocrystalline to electrode and preparation method thereof |
| CN105668607B (en) * | 2016-01-11 | 2018-02-06 | 天津师范大学 | A kind of preparation method of nano-sheet copper sulphide material |
| CN106057478B (en) * | 2016-05-11 | 2018-08-24 | 郑州大学 | In the preparation method and applications of the coarse CuS nanosheet array of nickel foam Surface Creation |
| CN108069393A (en) * | 2016-11-14 | 2018-05-25 | 中国科学院上海硅酸盐研究所 | A kind of hydrogenation Copper thin film and preparation method thereof |
| CN107758725A (en) * | 2017-11-18 | 2018-03-06 | 安徽师范大学 | A kind of copper sulfide semiconductor nano material, preparation method and applications |
| CN108682857B (en) * | 2018-06-14 | 2020-11-06 | 商丘师范学院 | Preparation method of porous flower flake lithium battery positive electrode material |
| CN108807914A (en) * | 2018-06-14 | 2018-11-13 | 商丘师范学院 | A kind of anode material of lithium battery of graphene coated and preparation method thereof |
| CN110127749B (en) * | 2019-05-28 | 2021-09-24 | 昆明理工大学 | Preparation method of cuprous sulfide nanoflower with copper defects |
| CN114182291B (en) * | 2021-12-23 | 2022-12-09 | 台州学院 | Preparation method of Fe-doped Ni3S2Ni2PNi12P5 compound |
-
2010
- 2010-02-08 CN CN2010101114035A patent/CN101792173B/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108033481A (en) * | 2018-02-05 | 2018-05-15 | 重庆交通大学 | The preparation method of orienting stephanoporate copper sulfide nano material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101792173A (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101792173B (en) | Chemical method for synthesizing flaky CuxSy nanocrystalline optoelectronic film controllably at low temperature | |
| CN104835654B (en) | A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof | |
| CN101805136B (en) | Chemical method for in situ preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass | |
| CN101845148B (en) | Preparation method of polyaniline nanofiber array | |
| CN101635315B (en) | Chemical method for preparing three-dimensional dendritic copper selenide nano-crystalline photoelectric film material | |
| CN102888630A (en) | Method for preparing nanometer aluminum or nanometer aluminum coating in low-temperature electro-deposition form by using ion liquid/additive system | |
| CN100545081C (en) | Dendritic silver selenide nano crystal thin film material and preparation method | |
| CN105562054A (en) | Preparation method of silver-doped two-dimensional graphite phase carbon nitride composite photocatalyst | |
| CN103145345B (en) | Chemical method for synthesising silver selenide semiconductor photoelectric film material in situ at room temperature | |
| CN103738946A (en) | Large area multifunction graphene film preparation method | |
| CN105870333A (en) | Flexible perovskite solar cell based on tungsten oxide and preparation method of solar cell | |
| CN102153288A (en) | Method for preparing copper disulfide thin film with preferred orientation | |
| CN102637777A (en) | Chemical preparation technology for solar cell light absorption layer Cu2O nano film | |
| CN101638777B (en) | Method for depositing copper sulphide nano film rapidly in low temperature | |
| CN110760874B (en) | Method for preparing iron oxide photo-anode film by using waste lithium iron phosphate battery | |
| Chen et al. | Morphology selective electrodeposition of Cu2O microcrystals on ZnO nanotube arrays as efficient visible-light-driven photo-electrode | |
| CN101863451B (en) | Method for preparing zinc oxide in three-dimensional nanostructure with cryogenic fluid method | |
| CN102315288A (en) | Thin film solar cell and preparation method thereof | |
| CN106981650A (en) | A kind of preparation method of nanoscale bismuth with elementary | |
| CN103247718B (en) | Chemical method for in-situ control and synthesis of AgCuS/Ag3CuS2 ternary semiconductor photoelectric thin-film material at normal temperature | |
| CN105097989A (en) | Method for preparing zinc sulfide photoelectric film | |
| CN103194784B (en) | A kind of method taking colloid as template controllable electric deposition and prepare nano-ZnO thin film | |
| CN103320828A (en) | Electrochemistry preparation method of hexamethylenetetramine doped nanometer zinc oxide thin film | |
| CN102887539B (en) | Chemical method for performing in-situ preparation of nano sulfur-tin-zinc-copper quaternary compound photovoltaic film | |
| CN105118888A (en) | Method for preparing cuprous-oxide photoelectric film through copper sulphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111214 Termination date: 20170208 |