CN105244408B - Method for preparing cuprous oxide photoelectric film by copper chloride - Google Patents
Method for preparing cuprous oxide photoelectric film by copper chloride Download PDFInfo
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- CN105244408B CN105244408B CN201410261274.6A CN201410261274A CN105244408B CN 105244408 B CN105244408 B CN 105244408B CN 201410261274 A CN201410261274 A CN 201410261274A CN 105244408 B CN105244408 B CN 105244408B
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- cuprous oxide
- electrode
- conductive glass
- photoelectric film
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a method for preparing a cuprous oxide photoelectric film by copper chloride, and belongs to the technical field of photoelectric film preparation. The method comprises the steps of firstly cleaning a substrate, then putting CuCl2.2H2O and sodium citrate into a solvent, carrying out constant potential deposition on a tin dioxide conductive glass substrate by adopting an electro-deposition method, and finally carrying out cleaning and drying to acquire the cuprous oxide photoelectric film. The method provided by the invention does not need a high-temperature high-vacuum condition, has low requirements for instruments and equipment, and is low in production cost, high in production efficiency and easy to operate. The prepared cuprous oxide photoelectric film has good continuity and uniformity. The new technology is easy to control composition and structure of a target product, and a preparation method, which is low in cost and capable of realizing industrialization, is provided for preparing the high-performance cuprous oxide photoelectric film.
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 chloride 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 nothing
Poison ring is protected, and 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.
The present invention prepares Red copper oxide with electrochemical deposition method in acid condition using copper chloride and sodium citrate system
Optoelectronic film, the method has low temperature, low cost, large-scale production prospect, can on the substrate of complex topography deposition film and
It is easy to the pattern and composition of control targe deposition film, the equal wide material sources of raw material are weighed and easy to operate, environmentally friendly.
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.
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
Red copper oxide optoelectronic film preparation method.
The present invention adopts electro-deposition method, and using Cu-lyt. and sodium citrate system Red copper oxide optoelectronic film material is prepared
Material, adopts tin dioxide conductive glass for substrate, with copper chloride and sodium citrate as raw material, with distilled water as solvent, with dilute salt
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 CuCl2·2H2O and sodium citrate are dissolved in solvent, the material in solution is uniformly mixed, and adjust pH
Value.Specifically, 1 part of sodium citrate can be substantially dissolved in 259 parts of distillation aqueous solvent, by 1.32 parts of CuCl2·2H2O
In being dissolved in above-mentioned solution, the material in solution is uniformly mixed, pH value of 10～20 parts of the dilute hydrochloric acid 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 1.32 parts of CuCl2·2H2O dissolves
In above-mentioned solution, the material in solution is uniformly mixed, pH value of 10～20 parts of the dilute hydrochloric acid to adjust solution can be added, make molten
The pH=2 of liquid.
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 chloride, 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 upper
State the tin dioxide conductive glass substrate for obtaining to be put in baking oven, dry at 100 DEG C, for masking；
B. 1 part of sodium citrate is substantially dissolved in 259 parts of distillation aqueous solvent, by 1.32 parts of CuCl2·2H2O is dissolved in above-mentioned
In solution, the material in solution is uniformly mixed, add pH value of 10～20 parts of the dilute hydrochloric acid to adjust solution, make the pH=of solution
2；
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, in -1.0V sedimentation potentials, room temperature, is not had
Have under conditions of stirring and deposit；
D. deposit after 30min, sample is taken out, with distilled water print is cleaned, be put in baking oven and be heated between 50～70 DEG C, protect
Warm 10～20min of time, is then cooled to room temperature taking-up so as to after natural drying, that is, obtain the Red copper oxide light of compact crystallization
Conductive film.
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| CN105244408B true CN105244408B (en) | 2017-05-03 |
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| CN105696047A (en) * | 2016-01-26 | 2016-06-22 | 太原理工大学 | Rapid preparation method for cuprous oxide nano-film |
| CN107020103B (en) * | 2017-03-20 | 2019-05-31 | 浙江工商大学 | A kind of iron oxide-molybdenum sulfide-cuprous oxide photocatalysis film and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
| CN103066345A (en) * | 2011-10-21 | 2013-04-24 | 中国科学院上海硅酸盐研究所 | Photoelectric chemical battery electrode and preparation method and application thereof |
| CN103364464A (en) * | 2013-07-31 | 2013-10-23 | 盐城工学院 | Construction method of photoelectric chemical sensor for detection of reduced glutathione |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103066345A (en) * | 2011-10-21 | 2013-04-24 | 中国科学院上海硅酸盐研究所 | Photoelectric chemical battery electrode and preparation method and application thereof |
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
| CN103364464A (en) * | 2013-07-31 | 2013-10-23 | 盐城工学院 | Construction method of photoelectric chemical sensor for detection of reduced glutathione |
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