CN105088301A - Method for preparing cuprous oxide optoelectronic film from copper nitrate - Google Patents
Method for preparing cuprous oxide optoelectronic film from copper nitrate Download PDFInfo
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- CN105088301A CN105088301A CN201410261268.0A CN201410261268A CN105088301A CN 105088301 A CN105088301 A CN 105088301A CN 201410261268 A CN201410261268 A CN 201410261268A CN 105088301 A CN105088301 A CN 105088301A
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Abstract
A method for preparing a cuprous oxide optoelectronic film from copper nitrate belongs to the technical field of optoelectronic film preparation and comprises the following steps: firstly, cleaning a substrate; then placing copper nitrate and sodium citrate into a solvent; adopting the electrodeposition method to conduct potentiostatic deposition on the obtained stannic oxide conductive glass substrate; and finally cleaning and drying to obtain the cuprous oxide optoelectronic film. The method does not need a high-temperature and high-vacuum condition, demands less on instrument equipment, and is low in production cost, high in production efficiency and easy to operate. The obtained cuprous oxide optoelectronic film is relatively good in continuity and uniformity. By adoption of the novel process, the ingredients and the structures of target products can be easily controlled, and the provided method for preparing the high-performance cuprous oxide optoelectronic film is low in cost and can be industrialized.
Description
Technical field
The invention belongs to optoelectronic film preparing technical field, particularly relate to a kind of method being prepared Red copper oxide optoelectronic film by cupric nitrate.
Background technology
The direct energy-gap semiconductor of Red copper oxide to be a kind of energy gap be 1.9 ~ 2.2eV, exciton can transport continuously in monocrystalline, it is made to have higher specific absorbance, become the important materials making photovoltaic converter, because it has unique light, magnetic performance, in solar energy converting, electronics, magnetic storing unit, bio-sensing and catalysis, have potential application, and asepsis environment-protecting, theoretical efficiency is about 20%, and cost is cheap, has good photovoltaic application prospect.
Prepare cuprous oxide film and can adopt thermal oxidation method, free-radical oxidn method, magnetron sputtering method, pulsed laser deposition and electrochemical deposition technique.Current employing electrodip process prepares Cu
2in the research of O film, mainly contain following three kinds of sedimentary systems available: (l) cupric nitrate system; (2) neutralized verdigris and cruel sour sodium system; (3) copper sulfate and acid system.Copper sulfate and acid system are the systems the most often used at present, mainly copper sulfate and lactic acid is used to be raw material, with sodium hydroxide condition pH value of solution, solution is in alkalescence, be heated to deposit film under 60 DEG C of conditions, it is wayward that complexing agent is that solution weighs, and under alkaline condition, bath stability is wayward, must heat treated, the inconvenience to operating band.
The present invention adopts cupric nitrate and Trisodium Citrate system to prepare Red copper oxide optoelectronic film with electrochemical deposition method in acid condition, the method has low temperature, low cost, scale operation prospect, the equal wide material sources of raw material, to weigh and easy and simple to handle, environmentally friendly, can at the deposited on substrates film of complex topography and pattern and the composition of being convenient to control objectives deposit film.
As method noted earlier, other method also has different defects.Related to the present invention also has as Publication about Document:
[1] swallow roc, Cai Shu, military defense soldier, electrochemical production p-type Cu
2the sign of O semiconductor film and performance thereof. XI AN JIAOTONG UNIVERSITY Subject Index 45.3 (2011): 121-124.
Article essentially describes the method utilizing copper sulfate and lactic acid etc. to do prepared using galvanic deposit and prepares cuprous oxide film, have studied the impact on cuprous oxide film stuctures and properties of complexing agent kind, sedimentation potential and solution ph. result shows: large in the film grain-size that to take lactic acid as the grain-size of the cuprous oxide film deposited in the electrolytic solution of complexing agent than with trolamine be deposits in the electrolytic solution of complexing agent, better crystallinity degree, density is higher.
[2]Wang,Lida,GuichangLiu,andDongfengXue，EffectsofsupportingelectrolyteongalvanicdepositionofCu
2Ocrystals，ElectrochimicaActa56.18(2011):6277-6283.
There is provided cupric ion to utilize the method for galvanic deposit to prepare cuprous oxide film with cupric nitrate herein, mainly have studied the impact of additive on film, result shows that the existence of additive not only also has impact to the Cheng Xiangyou impact of film to the structure of growing thin-film crystal.
[3]Mao-ChiaHuang,TsingHaiWang,Wen-ShengChang.Temperaturedependenceonp-Cu
2Othinfilmelectrochemicallydepositedontocoppersubstrate.AppliedSurfaceScience.02.085(2014):27301.
Prepare cuprous oxide film with copper sulfate and lactic acid as the method for prepared using galvanic deposit herein, mainly have studied the pattern of temperature on film and the impact of structure.
[4] Bi Wentuan, the progress of process for preparing Cu 2 O. Chemical Industry in Guangzhou, 37.8 (2009): 56-58.
Mainly describe herein and variously prepare the method for cuprous oxide film and present progress.
[5]Nian,Jun-Nan,Che-ChiaHu,andHsishengTeng,Electrodepositedp-typeCu
2OforH
2evolutionfromphotoelectrolysisofwaterundervisiblelightillumination.Internationaljournalofhydrogenenergy33.12(2008):2897-2903.
Copper sulfate is utilized to provide cupric ion herein, the method of galvanic deposit is used to prepare cuprous oxide film, mainly have studied the impact of depositing temperature on membrane structure, result surface obtains different membrane structures at different temperature, and high preferred orientation also there occurs change.
[6] disclosure of the invention CN102637777A, Yang Peizhi, from emerging, Yang Wen, Peng Liujun etc., a kind of chemical preparating process of solar cell light absorption layer Cu2O nano thin-film, 2012-05-04.
Employing copper sulfate and lactic acid are that the method for prepared using galvanic deposit prepares cuprous oxide film, solution sodium hydroxide adjust ph, prepare cuprous oxide film and carry out applying argon gas anneal.
Summary of the invention
The present invention in order to solve the deficiencies in the prior art, and invents preparation method that is a kind of and the diverse cupric nitrate optoelectronic film of the preparation method of prior art.
The present invention adopts electro-deposition method, utilizes Cu (NO
3)
2prepare Red copper oxide optoelectronic thin film material with Trisodium Citrate system, adopt tin dioxide conductive glass to be substrate, with Cu (NO
3)
2be raw material with Trisodium Citrate, take distilled water as solvent, be that assist medium is to adjust the pH value of solution with dust technology, by certain stoichiometric ratio obtain solution, adopt three electrode devicies, platinum electrode is as supporting electrode, saturated calomel electrode is as reference electrode, tin dioxide conductive substrate of glass is working electrode, uses transistor potentiostat to deposit under the condition of constant potential, obtains target product through specific depositing time.
Concrete preparation method of the present invention comprises the step of following order:
A. the cleaning of conductive glass substrate is carried out.Be that volume ratio trichloromethane put into by 20mm × 10mm × 4mm tin dioxide conductive glass: the solution of ethanol=5:1, ultrasonic cleaning 30min by size; Again sheet glass is put into volume ratio acetone: the solution of distilled water=5:1, ultrasonic cleaning 30min; Again in distilled water by conductive glass substrate sonic oscillation 30min; Being emitted in glass dish by tin dioxide conductive glass substrate obtained above sends in baking oven, dries, for masking at 100 DEG C;
B. by Cu (NO
3)
2be dissolved in solvent with Trisodium Citrate, make the material Homogeneous phase mixing in solution, and adjust ph.Specifically, can 1 part of Trisodium Citrate be fully dissolved in the distilled water solvent of 259 parts, by 1.84 parts of Cu (NO
3)
2be dissolved in above-mentioned solution, make the material Homogeneous phase mixing in solution, the pH value that dust technology 10 ~ 20 parts adjusts solution can be added;
C. pour in three electrode devicies by the solution that step b configures, take platinum electrode as supporting electrode, saturated calomel electrode is reference electrode, and tin dioxide conductive glass is Electrode, is linked to transistor potentiostat, deposits under the condition of constant potential;
D., after specific depositing time, sample is taken out, cleans print with distilled water, being put in baking oven is heated between 50 ~ 70 DEG C, soaking time 10 ~ 20min, and then cool to room temperature takes out, after making its seasoning, namely obtain the Red copper oxide optoelectronic film of compact crystallization.
The present invention does not need high temperature high vacuum condition, and raw material sources are extensive, weigh easy, and require low to plant and instrument, production cost is low, and production efficiency is high, easy handling.Gained Red copper oxide optoelectronic film has good continuity, compactness and homogeneity, and this novel method is that the high performance Red copper oxide optoelectronic film of preparation provides a kind of method that cost is low, can realize large-scale industrial production.
Accompanying drawing explanation
Accompanying drawing 1 is sedimentation potential is-1.0V, depositing time is 30min, the XRD figure spectrum of gained cuprous oxide film, result shows gained cuprous oxide film edge (110), (111), (200), the growth of (211) crystal face.
Embodiment
Embodiment 1
A. the cleaning of glass substrate: carry out cleaning tin dioxide conductive glass substrate (size is 20mm × 10mm × 4mm) as previously mentioned.
B. 1 part of Trisodium Citrate is fully dissolved in the distilled water solvent of 259 parts, by 1.84 parts of Cu (NO
3)
2be dissolved in above-mentioned solution, make the material Homogeneous phase mixing in solution, the pH value that dust technology 15 ~ 25 parts adjusts solution can be added, make the pH=2 of solution.
C. pour in three electrode devicies by the solution that step b configures, take platinum electrode as supporting electrode, saturated calomel electrode is reference electrode, tin dioxide conductive glass is Electrode, is linked to transistor potentiostat, in-1.0V sedimentation potential, normal temperature, deposits under not having the condition stirred.
D. after depositing 30min, taken out by sample, clean print, be put in baking oven and be heated between 50 ~ 70 DEG C, soaking time 10 ~ 20min with distilled water, then cool to room temperature takes out, and after making its seasoning, namely obtains the Red copper oxide optoelectronic film of compact crystallization.
Claims (1)
1. prepared a method for Red copper oxide optoelectronic film by cupric nitrate, comprise the step of following order:
A. the cleaning of conductive glass substrate is carried out; Be that volume ratio trichloromethane put into by 20mm × 10mm × 4mm tin dioxide conductive glass: the solution of ethanol=5:1, ultrasonic cleaning 30min by size; Again sheet glass is put into volume ratio acetone: the solution of distilled water=5:1, ultrasonic cleaning 30min; Again in distilled water by conductive glass substrate sonic oscillation 30min; Tin dioxide conductive glass substrate obtained above is put into baking oven, dries at 100 DEG C, for masking;
B. cupric nitrate and Trisodium Citrate are dissolved in solvent, make the material Homogeneous phase mixing in solution, and adjust ph; Specifically, can 1 part of Trisodium Citrate be fully dissolved in the distilled water solvent of 259 parts, by 1.84 parts of Cu (NO
3)
2be dissolved in above-mentioned solution, make the material Homogeneous phase mixing in solution, the pH value that dust technology 10 ~ 20 parts adjusts solution can be added;
C. pour in three electrode devicies by the solution that step b configures, take platinum electrode as supporting electrode, saturated calomel electrode is reference electrode, and tin dioxide conductive glass is Electrode, is connected to transistor potentiostat, deposits under the condition of constant potential;
D., after specific depositing time, taken out by sample, clean print, be put in baking oven and be heated between 50 ~ 70 DEG C, soaking time 10 ~ 20min with distilled water, then cool to room temperature takes out, and after making its seasoning, namely obtains Red copper oxide optoelectronic film.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803500A (en) * | 2016-04-05 | 2016-07-27 | 华南师范大学 | Petal-shaped cuprous oxide and preparation method and application thereof |
| CN107177876A (en) * | 2017-05-11 | 2017-09-19 | 云南民族大学 | A kind of method that electro-deposition prepares cuprous oxide lithium battery film material |
| CN109208020A (en) * | 2018-11-09 | 2019-01-15 | 广东顺德西安交通大学研究院 | A kind of electrochemical appliance and method synthesizing nano cuprous oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2313454A (en) * | 1938-05-24 | 1943-03-09 | Kansas City Testing Lab | Electrodeposition of cuprous oxides and baths therefor |
| CN1807688A (en) * | 2005-12-20 | 2006-07-26 | 厦门大学 | Process for preparing shape controllable cuprous oxide micro/nano crystal by electrochemical deposition |
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
-
2014
- 2014-06-13 CN CN201410261268.0A patent/CN105088301B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2313454A (en) * | 1938-05-24 | 1943-03-09 | Kansas City Testing Lab | Electrodeposition of cuprous oxides and baths therefor |
| CN1807688A (en) * | 2005-12-20 | 2006-07-26 | 厦门大学 | Process for preparing shape controllable cuprous oxide micro/nano crystal by electrochemical deposition |
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
Non-Patent Citations (3)
| Title |
|---|
| KEGAO LIU等: "Cuprous oxide thin films electrodeposited under conditions of different temperatures and pH values", 《OPTOELECTRONICS AND ADVANCED MATERIALS》 * |
| 石璐丹等: "电沉积工艺对氧化亚铜薄膜成相的影响", 《电镀与涂饰》 * |
| 苏旭: "Pt及Cu2O纳米薄膜的制备光催化性能分析", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803500A (en) * | 2016-04-05 | 2016-07-27 | 华南师范大学 | Petal-shaped cuprous oxide and preparation method and application thereof |
| CN105803500B (en) * | 2016-04-05 | 2018-04-10 | 华南师范大学 | A kind of petal-shaped cuprous oxide and its preparation method and application |
| CN107177876A (en) * | 2017-05-11 | 2017-09-19 | 云南民族大学 | A kind of method that electro-deposition prepares cuprous oxide lithium battery film material |
| CN109208020A (en) * | 2018-11-09 | 2019-01-15 | 广东顺德西安交通大学研究院 | A kind of electrochemical appliance and method synthesizing nano cuprous oxide |
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