CN105088301B - 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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- CN105088301B CN105088301B CN201410261268.0A CN201410261268A CN105088301B CN 105088301 B CN105088301 B CN 105088301B CN 201410261268 A CN201410261268 A CN 201410261268A CN 105088301 B CN105088301 B CN 105088301B
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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, more particularly to one kind to prepare Red copper oxide photoelectricity by copper nitrate thin
The method of film.
Background technology
Red copper oxide is the direct energy-gap semiconductor that a kind of energy gap is 1.9～2.2eV, and exciton can be even in monocrystalline
Transport continuously, make it have higher specific absorbance, become make photovoltaic converter important materials, because its have unique light,
Magnetic performance, there is potential application in terms of solar energy conversion, electronics, magnetic storage device, bio-sensing and catalysis, and
Asepsis environment-protecting, theoretical efficiency is about 20%, and cost is cheap, with good photovoltaic application prospect.
Preparing cuprous oxide film can adopt thermal oxidation method, free-radical oxidation method, magnetron sputtering method, pulsed laser deposition
And electrochemical deposition technique.At present Cu is prepared using electrodeposition process2In the research of O thin film, mainly there are following three kinds of sedimentary systems
It is available：(l) copper nitrate system；(2) Schweinfurt green and cruel sour sodium system；(3) copper sulfate and acid system.Copper sulfate and acid system
It is most currently used system, is raw material mainly using copper sulfate and lactic acid, with sodium hydroxide condition pH value of solution, solution exists
Alkalescence, deposition film under the conditions of being heated to 60 DEG C, it is wayward that chelating agent is that solution is weighed, and bath stability is not under alkalescence condition
It is easy to control, palpus heat treated, to operation with inconvenience.
The present invention prepares Red copper oxide with electrochemical deposition method in acid condition using copper nitrate and sodium citrate system
Optoelectronic film, the method has low temperature, low cost, large-scale production prospect, and the equal wide material sources of raw material are weighed and easy to operate,
It is environmentally friendly, deposition film and the pattern and composition of control targe deposition film can be easy on the substrate of complex topography.
As method noted earlier, other methods also have different defects.Related to the present invention also has following document：
[1] swallow roc, Cai Shu, military defense soldier, electrochemical process prepares p types Cu2The table of O semiconductive thin films and its performance
Levy. XI AN JIAOTONG UNIVERSITY Subject Index 45.3 (2011): 121-124.
Article essentially describes and does raw material using copper sulfate and lactic acid etc. to prepare Red copper oxide using the method for electro-deposition thin
Film, have studied the impact of chelating agent species, sedimentation potential and solution ph to cuprous oxide film structure and performance. result table
It is bright：The crystallite dimension ratio of the cuprous oxide film deposited in the electrolyte with lactic acid as chelating agent is with triethanolamine as complexation
The thin film crystallite dimension deposited in the electrolyte of agent is big, and better crystallinity degree, consistency is higher.
[2] Wang, Lida, Guichang Liu, and Dongfeng Xue, Effects of supporting
electrolyte on galvanic deposition of Cu2O crystals, Electrochimica Acta 56.18
(2011): 6277-6283.
There is provided copper ion with copper nitrate herein and prepare cuprous oxide film using the method for electro-deposition, mainly have studied addition
Impact of the agent to thin film, as a result shows the presence of additive not only to thin film into mutually having an impact the structure to growing thin-film crystal
Also have an impact.
[3]Mao-Chia Huang, TsingHai Wang, Wen-Sheng Chang. Temperature
dependence on p-Cu2O thin film electrochemically deposited onto copper
substrate. Applied Surface Science. 02.085 (2014):27301.
Herein cuprous oxide film is prepared using the method for electro-deposition as raw material with copper sulfate and lactic acid, mainly be have studied
Temperature is to the pattern of thin 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.
The various methods for preparing cuprous oxide film and present progress are mainly described herein.
[5]Nian, Jun-Nan, Che-Chia Hu, and Hsisheng Teng, Electrodeposited p-
type Cu2O for H2 evolution from photoelectrolysis of water under visible light
illumination. International journal of hydrogen energy 33.12 (2008): 2897-
2903.
Herein copper ion is provided using copper sulfate, using the method for electro-deposition cuprous oxide film is prepared, mainly be have studied
Impact of the depositing temperature to membrane structure, as a result surface obtains at different temperature different membrane structures, and crystal face takes
To also there occurs change.
[6] disclosure of the invention CN102637777A, Yang Peizhi, from emerging, Yang Wen, Peng Liujun etc., a kind of solar cell light
The chemical preparating process of absorbed layer Cu2O nano thin-films, 2012-05-04.
Adopt copper sulfate and lactic acid and prepare cuprous oxide film, solution sodium hydroxide using the method for electro-deposition for raw material
PH value is adjusted, preparing cuprous oxide film carries out applying argon gas annealing.
The content of the invention
The present invention has invented a kind of entirely different with the preparation method of prior art to solve the deficiencies in the prior art
Copper nitrate optoelectronic film preparation method.
The present invention adopts electro-deposition method, using Cu (NO3)2Red copper oxide optoelectronic film material is prepared with sodium citrate system
Material, adopts tin dioxide conductive glass for substrate, with Cu (NO3)2It is raw material with sodium citrate, with distilled water as solvent, with dilute nitre
Acid adjusts the pH value of solution for assist medium, solution is prepared by certain stoichiometric proportion, using three electrode assemblies, platinum electrode
Used as auxiliary electrode, used as reference electrode, tin dioxide conductive substrate of glass is working electrode to saturated calomel electrode, using crystal
Pipe potentiostat is deposited under conditions of constant potential, and through specific sedimentation time target product is obtained.
The concrete preparation method of the present invention is included following steps in sequence：
A. the cleaning of electro-conductive glass substrate is carried out.Size is put into for 20mm × 10mm × 4mm tin dioxide conductive glass
Volume ratio chloroform：Ethanol=5：In 1 solution, ultrasound wave cleaning 30min；Again sheet glass is put into into volume ratio acetone：Steam
Distilled water=5：In 1 solution, ultrasound wave cleaning 30min；Again by electro-conductive glass substrate sonic oscillation 30min in distilled water；Will
Tin dioxide conductive glass substrate obtained above is emitted in glass dish to be sent in baking oven, is dried at 100 DEG C, for masking
With;
B. by Cu (NO3)2It is dissolved in solvent with sodium citrate, the material in solution is uniformly mixed, and adjusts pH value.
Specifically, 1 part of sodium citrate can be substantially dissolved in 259 parts of distillation aqueous solvent, by 1.84 parts of Cu (NO3)2It is dissolved in
In above-mentioned solution, the material in solution is uniformly mixed, pH value of 10～20 parts of the dust technology to adjust solution can be added；
C. the solution that step b is configured is poured in three electrode assemblies, with platinum electrode as auxiliary electrode, saturated calomel electrode is
Reference electrode, tin dioxide conductive glass is Electrode, is linked to transistor potentiostat, is sunk under conditions of constant potential
Product；
D. after specific sedimentation time, sample is taken out, with distilled water print is cleaned, be put in baking oven and be heated to 50～70
Between DEG C, then 10～20min of temperature retention time is cooled to room temperature taking-up so as to after natural drying, that is, obtain the oxygen of compact crystallization
Change cuprous optoelectronic film.
It is of the invention not need high temperature high vacuum condition, raw material sources extensively, to weigh simplicity, it is low to instrument and equipment requirement, it is raw
Low cost is produced, production efficiency is high, it is easy to operate.Gained Red copper oxide optoelectronic film has preferable seriality, compactness and
Even property, this new method provides a kind of low cost, is capable of achieving on a large scale to prepare high performance Red copper oxide optoelectronic film
The method of industrialized production.
Description of the drawings
Accompanying drawing 1 is sedimentation potential for -1.0V, and sedimentation time is 30min, the XRD spectrum of gained cuprous oxide film, as a result
Show gained cuprous oxide film along (110), (111), (200), the growth of (211) crystal face.
Specific embodiment
Embodiment 1
A. the cleaning of glass substrate：Carry out as previously mentioned clean tin dioxide conductive glass substrate (size be 20mm ×
10mm×4mm)。
B. 1 part of sodium citrate is substantially dissolved in 259 parts of distillation aqueous solvent, by 1.84 parts of Cu (NO3)2It is dissolved in
In stating solution, the material in solution is uniformly mixed, pH value of 15～25 parts of the dust technology to adjust solution can be added, make solution
pH=2。
C. the solution that step b is configured is poured in three electrode assemblies, with platinum electrode as auxiliary electrode, saturated calomel electrode
For reference electrode, tin dioxide conductive glass is Electrode, is linked to transistor potentiostat, in -1.0V sedimentation potentials, often
Temperature, without deposition under conditions of stirring.
D. deposit 30min after, sample is taken out, clean print with distilled water, be put in baking oven be heated to 50～70 DEG C it
Between, then 10～20min of temperature retention time is cooled to room temperature taking-up so as to after natural drying, that is, the oxidation for obtaining compact crystallization is sub-
Bronzing conductive film.
Claims (1)
1. a kind of method that Red copper oxide optoelectronic film is prepared by copper nitrate, including following steps in sequence：
A. the cleaning of electro-conductive glass substrate is carried out；Size is put into into volume for 20mm × 10mm × 4mm tin dioxide conductive glass
Compare chloroform：Ethanol=5：In 1 solution, ultrasound wave cleaning 30min；Again sheet glass is put into into volume ratio acetone：Distilled water=
5：In 1 solution, ultrasound wave cleaning 30min；Again by electro-conductive glass substrate sonic oscillation 30min in distilled water；Will be above-mentioned
The tin dioxide conductive glass substrate for obtaining is put in baking oven, is dried at 100 DEG C, for masking；
B. 1 part of sodium citrate is substantially dissolved in into formation solution a in 259 parts of distillation aqueous solvent, by 1.84 parts of Cu (NO3)2Dissolving
In above-mentioned solution a, each material is uniformly mixed, pH value of 10～20 parts of the dust technology to adjust solution can be added, form solution
b；
C. the solution b that step b is configured is poured in three electrode assemblies, with platinum electrode as auxiliary electrode, saturated calomel electrode is ginseng
Than electrode, tin dioxide conductive glass is Electrode, is connected to transistor potentiostat, is deposited under conditions of constant potential；
D. after specific sedimentation time, sample is taken out, with distilled water print is cleaned, be put in baking oven be heated to 50～70 DEG C it
Between, then 10～20min of temperature retention time is cooled to room temperature taking-up so as to after natural drying, that is, obtain Red copper oxide photoelectricity thin
Film.
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| CN201410261268.0A CN105088301B (en) | 2014-06-13 | 2014-06-13 | Method for preparing cuprous oxide optoelectronic film from copper nitrate |
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| CN201410261268.0A CN105088301B (en) | 2014-06-13 | 2014-06-13 | Method for preparing cuprous oxide optoelectronic film from copper nitrate |
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| CN105088301A CN105088301A (en) | 2015-11-25 |
| CN105088301B true CN105088301B (en) | 2017-05-03 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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 |
|---|
| Cuprous oxide thin films electrodeposited under conditions of different temperatures and pH values;KEGAO LIU等;《OPTOELECTRONICS AND ADVANCED MATERIALS》;20160430;第10卷(第3-4期);第249-252页 * |
| Pt及Cu2O纳米薄膜的制备光催化性能分析;苏旭;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20100115;第50页倒数第1段，第51页，第54页倒数第1段 * |
| 电沉积工艺对氧化亚铜薄膜成相的影响;石璐丹等;《电镀与涂饰》;20150215;第37卷(第2期);第24-27页 * |
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