CN101774629B - Controllable preparation method of p-type and n-type cuprous oxide film by using hydrothermal method - Google Patents
Controllable preparation method of p-type and n-type cuprous oxide film by using hydrothermal method Download PDFInfo
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- CN101774629B CN101774629B CN2010100289210A CN201010028921A CN101774629B CN 101774629 B CN101774629 B CN 101774629B CN 2010100289210 A CN2010100289210 A CN 2010100289210A CN 201010028921 A CN201010028921 A CN 201010028921A CN 101774629 B CN101774629 B CN 101774629B
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Abstract
The invention relates to a controllable preparation method of a p-type and n-type cuprous oxide film by using a hydrothermal method. In the invention, the needed semiconductor cuprous oxide film of different conductive types (p-type or n-type) is obtained by controlling a pH value of aqueous solution in a reactant. The method comprises the following steps of: firstly preparing bivalent copper ion salt solution of certain concentration; adjusting the pH value of the solution by diluted acid and ammonia water; placing the prepared bivalent copper ion salt solution and a cleaned pure metal copper sheet into an autoclave, wherein the copper sheet is completely immersed in the solution; and keeping the autoclave at 100-200 DEG C to react for 0.5-20 h to obtain the needed cuprous oxide film, wherein the conductive type of the cuprous oxide film prepared under the subacidity condition is the n-type, while the conductive type of the cuprous oxide film prepared under the neutral or the alkaline condition is the p-type. The cuprous oxide film of different conductive types obtained by the simple hydrothermal preparation method has wide application in homojunction semiconductor solar cells.
Description
Technical field
The present invention relates to the controllable method for preparing of different conduction-types semiconductor film material.Belong to have transmitter, the preparation method of application prospect nanostructure cuprous oxide thin film material such as nano electron device, lithium ion battery, homojunction photovoltaic device and low-cost thin-film solar cells and catalyzer, sterilant, algicide.
Background technology
Red copper oxide (Cu
2O) be a kind of non-stoichiometric (nonstoichiometric) brick-red semi-conductor (Z.C.Orel, A.Anlovar, G.Drai, et al.Cryst.Growth Des.2007,7,453-458).Usually all is the p type with traditional method such as the cuprous oxide film conduction type that thermal oxidation method prepares, this be since the ratio of this film copper and oxygen less than 2: 1, and the existence that has the copper vacancy to fall into form (A.E.Rakhshani.Solid-StateElectron.1986,29,7-17).N type Red copper oxide by doping techniques preparation not noticeable always (A.A.Berrezin, F.L Weichman.Solid State Commun.1981,37,157-160.).To so far, also have only a few method for preparing n type Red copper oxide be seen in report (C.M McShane, K.S.Choi.J.Am.Chem.Soc.2009,131,2561-2569.).The formation condition that this a few preparation method's a common feature is a Red copper oxide all is a sour environment.And by in alkaline environment, using chemical deposition (M.T.S.Nair, L.Guerrero, O.L.Arenas, P.K.Nair.App.Surf.Sci.1999,150,143-151.), electrodip process (J.N.Nian, C.C.Hu, H.Teng.Int.J.Hydrogen Energy.2008,33,2897-2903) Zhi Bei Red copper oxide presents p N-type semiconductorN feature.
Hydrothermal method (hydrothermal method) claim hydrothermal method again.Be meant that be solvent with water in the pressurized vessel of sealing, the chemical reaction that under high-temperature and high-pressure conditions, carries out.Because the airtight and conserve energy of reaction system, hydrothermal method be a kind of help environment and economic good method (J.H.Lee, N.Kumagai, T.Watanabe, M.Yoshimura.Solid State Ionics.2002,151,41-45).And the product that generates through hydrothermal method does not generally need after annealing to handle.The applicant utilizes hydrothermal method, by the control pH value of aqueous solution, has prepared the controlled cuprous oxide film with different conduction-types feature.Wherein the cuprous oxide film of preparing under solutions of weak acidity is a n type optical response semiconductor, is p type optical response semiconductor under alkaline condition.This process has ubiquity, and simple, easy row can be realized large-scale production.The product that wherein prepares can provide the basis for further developing homogeneity Red copper oxide p/n knot.
Summary of the invention
The objective of the invention is to obtain the cuprous oxide film of needed different conduction-types (p or n type) by pH value of aqueous solution in the control reactant.
Principle of the present invention is:
In the aqueous solution, following disproportionation reaction can take place in zero-valent metal copper and bivalent cupric ion:
Cu+Cu
2++H
2O—————→Cu
2O+2H
+ …………………(1)。
As can be seen, along with the carrying out of reaction, the pH value of solution meeting reduction progressively, and Red copper oxide dissolution equilibrium in the aqueous solution can be expressed from the next:
In the strong more solution of acidity, the following formula reaction is carried out left more, and monovalence copper (Cu+) ion is many more in the solution, that is Red copper oxide solubleness in acidic solution is big more, therefore, in the less strong acid solution of pH value of solution value, is difficult to have Red copper oxide to form.The reaction of (2) formula is carried out to the right when the pH of solution value is slightly acidic, and Red copper oxide solubleness reduces, so as elemental copper and Cu
2+Ionic reaction makes the Cu in the solution
+After ionic concn reaches capacity, have Red copper oxide and be deposited on copper surface.Because Red copper oxide is a kind of conductor oxidate with subsurface defect of non-stoichiometric, this moment, reaction soln was acid, Cu in the solution
+Higher and the OH of ionic concn
-Ionic concentration is very low, and the atom proportioning that may generate copper and oxygen has the n N-type semiconductorN Red copper oxide of oxygen defect greater than 2 (stoichiometric(al) is 2: 1).The experimental result that this and many Red copper oxide that generate in acidic solution are the n N-type semiconductorN is consistent.When the pH of solution value when being neutral or alkaline, the Cu in the solution is further carried out in the reaction of (2) formula to the right
+Ionic concn further reduces, and Red copper oxide solubleness becomes littler, and the OH in the solution at this moment
-Ionic concn is relatively large, and the atom proportioning that may generate copper and oxygen is less than 2 the p N-type semiconductorN Red copper oxide with copper defective.The experimental result that this and many Red copper oxide that generate in basic solution are the p N-type semiconductorN is consistent.
Therefore, by the pH value of solution in the control reactant, utilize hydrothermal method can obtain the Red copper oxide semiconductor film of needed p type or n type easily.
The scheme that realizes the object of the invention is:
Controllable method for preparing with Red copper oxide semiconductor film of different conduction-types, it is characterized in that preparing with hydrothermal method, its method is to prepare certain density bivalent cupric ion salts solution with the precursor of copper earlier, come the pH value of regulator solution by diluted acid and ammoniacal liquor, a certain amount of, solution that configures and the pure metal copper sheet that cleans up are inserted in the autoclave, and copper sheet all is immersed in this solution.Autoclave is remained on certain thermotonus for some time.Can obtain needed cuprous oxide film.Wherein the conduction type of the cuprous oxide film for preparing under solutions of weak acidity is the n type, is the p type under neutrality or alkaline condition.
In the solution of the present invention, the precursor of employed copper is water miscible cupric salt and pure metal copper sheet, and described mantoquita is copper sulfate, neutralized verdigris, cupric nitrate or cupric chloride, and copper sheet purity is more than 99%, and the concentration of cupric salt is 1 * 10
-4～1M, preferred concentration are 5 * 10
-4～5 * 10
-3M, optimum concn is 0.001M.
In the solution of the present invention, employed diluted acid is dilute sulphuric acid, dilute acetic acid or dilute hydrochloric acid, and concentration is 0.001～1.5M, and preferred concentration is 0.05～1M, and optimum concn is 0.5M; The mass percent concentration of ammoniacal liquor is 0.1%～5%, and the preferred mass percentage concentration is 1%～3%, and the best in quality percentage concentration is 2%.
In the solution of the present invention, the variable range of pH value is between 3 to 12.The conduction type of the cuprous oxide film that the pH value prepares under the condition between the 3-5 is the n type, and the conduction type of the cuprous oxide film that the pH value prepares under the condition between the 7-12 is the p type.
In the solution of the present invention, the temperature of autoclave remains between 100-200 ℃, and preferred temperature remains between 120-180 ℃, and optimum temps is 160 ℃; Reaction times is 0.5-20 hour, and Best Times is 8 hours.
Description of drawings
Fig. 1. the XRD figure of cuprous oxide film
Fig. 2. the SEM picture of the cuprous oxide film of blank pure metal copper sheet and preparation
(a wherein
1) blank pure metal copper sheet; (b
1), (c
1), (d
1), (e
1), (f
1), (g
1) be respectively that the pH value of solution value is: 1,3,5,7, the cuprous oxide film of preparation in 9,11 o'clock.
Fig. 3 .pH value equals 3 (a respectively
2), 5 (b
2), 6 (c
2), 7 (d
2), 9 (e
2), 11 (f
2) time open circuit photovoltage graphic representation of preparation-obtained sample under the pulse radiation of visible light.
Fig. 4 .pH equals 6 (a respectively
3), 3 (b
3), 5 (c
3), 7 (d
3), 9 (e
3), 11 (f
3) time the prepared short-circuit photocurrent graphic representation of cuprous oxide film under radiation of visible light.
Fig. 5. p type (a under the radiation of visible light
4) and n type (b
4) the photo-generated carrier transfer synoptic diagram of cuprous oxide film in solution.
Embodiment
Further specify the inventive method and effect below by embodiment.
Embodiment 1:
The cuprous oxide film preparation, preparation process is:
1, the cleaning of substrate: with pure metal copper sheet (2.5 * 6cm
2) be immersed in the dilute hydrochloric acid more than 10 minutes, take out, with big water gaging flushing, carefully scrub with banister brush again, then, use deionized water, acetone, each ultrasonic cleaning of alcohol 10 minutes, taking-up dries up afterwards standby;
2, the CuSO of preparation 0.001M
4Solution 80ml does not add any diluted acid or ammoniacal liquor, and recording the pH value of solution value with pH meter is 5, and solution is all poured in the autoclave.Again the pure metal copper sheet that cleans up is inserted in the autoclave, allow copper sheet all be immersed in the solution during placement;
3, autoclave is put into air dry oven, setting the temperature inside the box is 160 ℃, and the reaction times is 8 hours;
4, relief autoclave naturally cooling is finished in reaction, takes out reacted copper sheet, and it is brick-red to find at this moment before the reaction that flavous pure metal copper sheet has become, and this layer is exactly the cuprous oxide film of preparation with the film of color.Its XRD figure sheet as shown in Figure 1.
Fig. 3 (b
1) shown the open circuit photovoltage curve of this cuprous oxide film under the pulse radiation of visible light.In the moment that light source begins to shine, produce negative open circuit photovoltage; This is typical n type optical response semiconductor feature.Fig. 4 (c
3) shown the short-circuit photocurrent curve of this cuprous oxide film under radiation of visible light, under the light source irradiation condition, produced the anode photoelectric current, this also is typical n type optical response semiconductor feature.Therefore.In the pH value is that cuprous oxide film prepared under 5 conditions is the n N-type semiconductorN.
Fig. 5 has shown that the photo-generated carrier at p type and n N-type semiconductorN Red copper oxide solution interface place under radiation of visible light shifts synoptic diagram.Under radiation of visible light, the electronics of p N-type semiconductorN Red copper oxide is to flow of solution as shown in Figure 5, and the hole is then to the Red copper oxide bulk flow, thus generation cathode photo current and positive photovoltage.The electron hole situation of n N-type semiconductorN Red copper oxide under radiation of visible light is then just in time opposite, and the photoelectric current of generation and photovoltage are also just in time opposite.
Embodiment 2:
Except with CuSO
4Solution replaces to neutralized verdigris (Cu (CH
3COOH)
2), outside cupric chloride or the copper nitrate solution, keep operational condition and step all among the embodiment 1 constant, also prepared n type cuprous oxide film, its photoelectric properties are similar with embodiment 1.
Embodiment 3:
With CuSO among the embodiment 1
4Solution is by dripping dilute sulphuric acid (0.5M), and adjusting its pH value is 3, and operational condition and step that other are all are constant.Fig. 3 (a
1) having shown the open circuit photovoltage curve of this cuprous oxide film under the pulse radiation of visible light, its photovoltage is a negative value.Fig. 4 (c
2) shown the short-circuit photocurrent curve of this cuprous oxide film under radiation of visible light, photoelectric current be on the occasion of, be anode photoelectric current feature.Can prepare n type cuprous oxide film, its photoelectric properties are also similar with embodiment 1.Above-mentioned dilute sulphuric acid is replaced with dilute hydrochloric acid, obtain similar result.
Embodiment 4:
With CuSO among the embodiment 1
4Solution is by dropping ammonia (2%), and adjusting its pH value is 9, and operational condition and step that other are all are constant.Fig. 3 (e
1) shown the open circuit photovoltage curve of this cuprous oxide film under the pulse radiation of visible light, photovoltage be on the occasion of.Fig. 4 (f
2) shown the short-circuit photocurrent curve of this cuprous oxide film under radiation of visible light, be the cathode photo current feature.Can prepare p type cuprous oxide film.PH value by the dropping ammonia regulator solution is that 7,10,11,12 grades all can get p type cuprous oxide film.
Embodiment 5:
With CuSO among the embodiment 1
4Solution replaces to Cupric Chloride Solution (0.005M), and by dropping ammonia (2%), adjusting its pH value is 7,9,10,11, and 12 etc., operational condition and step that other are all are constant, all can get p type cuprous oxide film.Short-circuit photocurrent curve under the radiation of visible light of these films and the d among Fig. 4
3, e
3, f
3Similar, photoelectric current is a negative value, and along with the increase of pH value, the photoelectric current absolute value increases.
Embodiment 6:
With CuSO among the embodiment 1
4Solution replaces to copper nitrate solution (0.01M), is 3,4,5,6 etc. by dripping dilute acetic acid (0.01M), adjusting its pH value, and operational condition and step that other are all are constant, all can get n type cuprous oxide film.Short-circuit photocurrent curve under the radiation of visible light of these films and the b among Fig. 4
3, c
3Similar, photoelectric current be on the occasion of, and along with the increase of pH value, the photoelectricity flow valuve reduces.
Embodiment 7:
Step according to embodiment 1 prepares cuprous oxide film, wherein CuSO
4Strength of solution increases to 0.005M, is 3,5,7,9,11 etc. by dripping dilute acetic acid (0.01M) or ammoniacal liquor (2%), adjusting its pH value, wherein CuSO
4Solution and copper sheet are put into autoclave, and temperature is 180 ℃, and the reaction times is 4 hours, and operational condition and step that other are all are constant, can get n or p type cuprous oxide film.The variation tendency and the variation tendency among Fig. 3 of the open circuit photovoltage under the radiation of visible light of these films are similar, promptly along with the pH value increases, photovoltage shows n N-type semiconductorN feature earlier, and the photovoltage absolute value reduces gradually, show p type feature then under alkaline condition, the photovoltage value increases again gradually.Similar among short-circuit photocurrent variation tendency and Fig. 4, under acidic conditions, show as the anode photoelectric current, show n N-type semiconductorN feature, and numerical value reduces with the pH increase, under alkaline condition, obtain cathode photo current, show p N-type semiconductorN feature, along with the increase of pH value, the photoelectric current absolute value increases.
Claims (10)
1. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types is characterized in that using Hydrothermal Preparation, and its method is to prepare 1 * 10 with the precursor of copper earlier
-4The bivalent cupric ion salts solution of～1M concentration, come the pH value of regulator solution by diluted acid and ammoniacal liquor, bivalent cupric ion salts solution that configures and the pure metal copper sheet that cleans up are inserted in the autoclave, copper sheet all is immersed in this solution, the temperature of autoclave is remained on 100-200 ℃ of reaction 0.5-20 hour, promptly obtain cuprous oxide film, the conduction type of the cuprous oxide film for preparing between pH value 3-5 is the n type, and the conduction type of the cuprous oxide film that the pH value prepares between 7-12 is the p type.
2. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, it is characterized in that, the precursor of employed copper is water miscible mantoquita and pure metal copper sheet, described mantoquita is copper sulfate, neutralized verdigris, cupric nitrate or cupric chloride, and described pure metal copper sheet purity is more than 99%.
3. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, the concentration that it is characterized in that described bivalent cupric ion salts solution is 5 * 10
-4～5 * 10
-3M.
4. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, the concentration that it is characterized in that described bivalent cupric ion salts solution is 0.001M.
5. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, it is characterized in that employed diluted acid is dilute sulphuric acid, dilute acetic acid or dilute hydrochloric acid, concentration is 0.001～1.5M, and the mass percent concentration of employed ammoniacal liquor is 0.1～5%.
6. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, it is characterized in that employed diluted acid is dilute sulphuric acid, dilute acetic acid or dilute hydrochloric acid, concentration is 0.05～1M, and the mass percent concentration of employed ammoniacal liquor is 1%～3%.
7. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1 is characterized in that described dilute acid concentration is 0.5M.
8. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1, the mass percent concentration that it is characterized in that described ammoniacal liquor is 2%.
9. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1 is characterized in that the temperature of autoclave remains on 120-180 ℃, reacts 0.5-20 hour.
10. the controllable method for preparing of the Red copper oxide semiconductor film of different conduction-types as claimed in claim 1 is characterized in that the temperature of autoclave remains on 160 ℃, and the reaction times is 8 hours.
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| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN102284293B (en) * | 2011-06-24 | 2013-03-13 | 余颖 | Cu/Cu2O film material for reducing CO2 into organic fuel under catalysis |
| CN102503169B (en) * | 2011-08-03 | 2013-11-13 | 太原理工大学 | Preparation method of zinc oxide/cuprous oxide heterojunction |
| CN102583499A (en) * | 2012-01-11 | 2012-07-18 | 哈尔滨工业大学 | Preparation method for cuprous oxide micron/nano crystal with controllable morphology |
| CN103373739A (en) * | 2012-04-18 | 2013-10-30 | 宁波大学 | Hydrothermal preparation method of cuprous oxide crystal |
| CN103400975B (en) * | 2013-08-13 | 2015-10-14 | 西南大学 | Cu 2the preparation method of O secondary cell anode material |
| CN105525349B (en) * | 2015-12-31 | 2018-09-07 | 中国科学院半导体研究所 | A kind of preparation method of cuprous oxide monocrystal thin films |
| CN108796532B (en) * | 2017-05-03 | 2020-06-16 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode, preparation method thereof and application thereof in photocatalysis |
| CN108336187B (en) * | 2018-02-13 | 2019-11-26 | 桂林理工大学 | A kind of Ag/Cu2The preparation method of O hetero-junctions nano thin-film |
| CN109087967A (en) * | 2018-08-10 | 2018-12-25 | 暨南大学 | A kind of cuprous oxide film and the preparation method and application thereof |
| CN110186986B (en) * | 2019-06-21 | 2021-02-02 | 福建工程学院 | Enzyme-free glucose electrochemical sensor and detection method thereof |
| CN111153427A (en) * | 2020-01-14 | 2020-05-15 | 江苏海洋大学 | Preparation method of cuprous oxide film with controllable shape |
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