CN102312231B - Process for preparing CuCrO2 film by using sol-gel method - Google Patents

Process for preparing CuCrO2 film by using sol-gel method Download PDF

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CN102312231B
CN102312231B CN 201110295855 CN201110295855A CN102312231B CN 102312231 B CN102312231 B CN 102312231B CN 201110295855 CN201110295855 CN 201110295855 CN 201110295855 A CN201110295855 A CN 201110295855A CN 102312231 B CN102312231 B CN 102312231B
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film
cucro
substrate
gel method
burning
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CN102312231A (en
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王金梅
郑培超
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Chongqing University of Post and Telecommunications
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Abstract

The invention discloses a process for preparing a CuCrO2 film by using the sol-gel method. The process comprises the following steps: a, preparing a precursor solution; b, coating a film on a clean substrate by using the method of spin coating; c, pre-burning the substrate; d, sintering the substrate at high temperature. The method for preparing the CuCrO2 film in the invention has the advantages of low energy consumption, simple technology, no need for any vacuum condition, low production cost, capacity of forming a large film on a substrate with any shape, minimizing particle size and reducing reaction temperature, and high film coating efficiency; the method enables a prepared sample to have good chemical uniformity, and repeatability of experimental results of the method is achieved.

Description

A kind of Prepared by Sol Gel Method CuCrO that uses 2The method of film
Technical field
The present invention relates to a kind of CuCrO 2The preparation method of film, particularly a kind of Prepared by Sol Gel Method CuCrO that uses 2The method of film.
Background technology
Kawazoe in 1997 etc. have reported delafossite structure oxide compound CuAlO 2Film is that (Transparent Conducting Oxide TCO), thereby has evoked the research boom of delafossite structure oxide compound to a kind of broad-band gap p-type transparent conductive oxide.Delafossite structure oxide compound ABO 2(Eg＞3.1eV), wherein A is monovalent metallic ions such as Ag, Cu, and B is trivalent metal ions such as Al, Cr, Y, Sc for wide band gap semiconducter.Delafossite structure p-type transparent conductive oxide film is the novel material that a class has wide application prospect in person in electronics, because it can receive much concern with " transparent devices " that the n-TCO film forms truly.At present, the preparation method of delafossite structure p-TCO film has PLD, sputter (Sputtering) method, metal organic chemical vapor deposition (Metal Organic Chemical Vapor Deposition, MOCVD) equal vacuum technology, but cost costliness, complicated operation.
Along with the continuous expansion of Application Areas, physical properties and the chemical property of TCO film are had higher requirement.Therefore, must update the preparation method of TCO film, and the direction of making great efforts should embody and improves film performance, reduces temperature of reaction, improves control accuracy, reduces preparation cost and adapt to trend such as integrated.
Summary of the invention
In view of this, the purpose of this invention is to provide simple, the lower-cost CuCrO of a kind of operation 2Method for manufacturing thin film.
The objective of the invention is to be achieved through the following technical solutions: a kind of Prepared by Sol Gel Method CuCrO that uses 2The method of film may further comprise the steps:
A, be 1: 1 weighing venus crystals and chromium nitrate by the mol ratio of copper, chromium, and venus crystals and chromium nitrate powder joined in the 10mL propionic acid successively, under 60 ℃～70 ℃, be stirred to dissolving fully, obtaining volumetric molar concentration is the precursor solution that mixes of 0.2mol/L;
B is with solution employing spin-coating method plated film on the substrate of cleaning of gained among a;
C puts into 300～600 ℃ tube furnace pre-burning with b step gained film, removes water, solvent and organism in the film, obtains inorganic thin film;
D, the inorganic thin film that step c pre-burning is obtained places tube furnace, at N 2Be warming up to 800～1000 ℃ with the speed that is not higher than 20 ℃/hour in the atmosphere, be incubated 1 hour then, furnace cooling namely gets CuCrO 2Film.
Further, among the step b, described substrate is Al 2O 3(0001) (sapphire) monocrystal chip;
Further, among the step c, the pre-burning time of film being put into tube furnace is 20～30 minutes;
Further, step b and c can carry out 3-5 time repeatedly.
Beneficial effect of the present invention: adopt method of the present invention to prepare CuCrO 2Film, energy consumption is low, technology is simple, without any need for vacuum condition, production cost is relatively low, can be on the matrix of arbitrary shape large-area film forming, refinement of particle size reduces temperature of reaction, plated film efficient height, the sample chemical good uniformity of preparing, experimental result possesses repeatability.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is further described:
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is for adopting the CuCrO of embodiment 2 described method preparations 2Film uses the XRD figure spectrum that obtains after the test of Phillips X ' Pert type X-ray diffraction (XRD) instrument.
Embodiment
As shown in Figure 1:
Embodiment 1:
At first make with ordinary method or buy venus crystals, chromium nitrate from market, finish preparation according to the following steps order then:
A joins the venus crystals of 0.4033g and the chromium nitrate of 0.8084g in the 10mL propionic acid, stirs down at 60 ℃, to dissolving fully, obtains the precursor solution that mixes of 0.2mol/L;
B adopts spin-coating method (spin-coating) at the Al of cleaning the solution after stirring 2O 3Plated film on the substrate, rotating speed are 5000rmp, and the time is 60 seconds;
C puts into 300 ℃ of pre-burnings of tube furnace 20 minutes with film, removes water, solvent and organism in the film, obtains inorganic thin film;
For making thin film layer evenly and having suitable thickness, above-mentioned steps b, c carry out 4 times repeatedly;
D, the inorganic thin film that pre-burning is obtained places tube furnace, at N 2Speed with 10 ℃/hour in the atmosphere is warming up to 900 ℃, is incubated 1 hour then, and furnace cooling namely gets CuCrO 2Film.
Embodiment 2:
At first make with ordinary method or buy venus crystals, chromium nitrate from market, finish preparation according to the following steps order then:
A joins the venus crystals of 0.4033g and the chromium nitrate of 0.8084g in the 10mL propionic acid, stirs down at 70 ℃, to dissolving fully, obtains the precursor solution that mixes of 0.2mol/L;
B adopts spin-coating method (spin-coating) at the Al of cleaning the solution after stirring 2O 3Plated film on the substrate, rotating speed are 5000rmp, and the time is 60 seconds;
C puts into 400 ℃ of pre-burnings of tube furnace 25 minutes with film, removes water, solvent and organism in the film, obtains inorganic thin film;
For making thin film layer evenly and having suitable thickness, above-mentioned steps b, c carry out 3 times repeatedly;
D, the inorganic thin film that pre-burning is obtained places tube furnace, at N 2Speed with 15 ℃/hour in the atmosphere is warming up to 900 ℃, is incubated 1 hour then, and furnace cooling namely gets CuCrO 2Film.
Embodiment 3:
At first make with ordinary method or buy venus crystals, chromium nitrate from market, finish preparation according to the following steps order then:
A joins the venus crystals of 0.4033g and the chromium nitrate of 0.8084g in the 10mL propionic acid, stirs down at 65 ℃, to dissolving fully, obtains the precursor solution that mixes of 0.2mol/L;
B adopts spin-coating method (spin-coating) at the Al of cleaning the solution after stirring 2O 3Plated film on the substrate, rotating speed are 5000rmp, and the time is 60 seconds;
C puts into 500 ℃ of pre-burnings of tube furnace 30 minutes with film, removes water, solvent and organism in the film, obtains inorganic thin film;
For making thin film layer evenly and having suitable thickness, above-mentioned steps b, c carry out 5 times repeatedly;
D, the inorganic thin film that pre-burning is obtained places tube furnace, at N 2Speed with 18 ℃/hour in the atmosphere is warming up to 900 ℃, is incubated 1 hour then, and furnace cooling namely gets CuCrO 2Film.
Embodiment 4:
At first make with ordinary method or buy venus crystals, chromium nitrate from market, finish preparation according to the following steps order then:
A joins the venus crystals of 0.4033g and the chromium nitrate of 0.8084g in the 10mL propionic acid, stirs down at 68 ℃, to dissolving fully, obtains the precursor solution that mixes of 0.2mol/L;
B adopts spin-coating method (spin-coating) at the Al of cleaning the solution after stirring 2O 3Plated film on the substrate, rotating speed are 5000rmp, and the time is 60 seconds;
C puts into 600 ℃ of pre-burnings of tube furnace 30 minutes with film, removes water, solvent and organism in the film, obtains inorganic thin film;
For making thin film layer evenly and having suitable thickness, above-mentioned steps b, c carry out 4 times repeatedly;
D, the inorganic thin film that pre-burning is obtained places tube furnace, at N 2Speed with 20 ℃/hour in the atmosphere is warming up to 1000 ℃, is incubated 1 hour then, and furnace cooling namely gets CuCrO 2Film.
As shown in Figure 2, to the CuCrO of embodiment three gained 2Film uses Phillips X ' Pert type X-ray diffraction (XRD) instrument to test, the XRD figure spectrum that obtains, and the X-coordinate among Fig. 2 is that diffraction angle, ordinate zou are relative intensity, * is the peak of substrate.By the position of each diffraction peak in the XRD figure and relative intensity as can be known, thin film crystallization is very good, does not have any dephasign and generates, and be high C-axis orientation, and this polycrystalline material is the 3R-CuCrO of delafossite structure 2The polycrystalline phase.
Obviously, those skilled in the art can be to delafossite structure CuCr of the present invention 1-xTM xO 2The material of (0≤x≤0.20, TM is transition-metal Fe, Co, Ni, Mn etc.) dilute magnetic semiconductor material and preparation thereof carries out various changes and modification and does not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment the present invention is had been described in detail, but those of ordinary skill in the art makes amendment to technical scheme of the present invention or is equal to replacement, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (4)

1. use Prepared by Sol Gel Method CuCrO for one kind 2The method of film is characterized in that: may further comprise the steps:
A is 1: 1 weighing venus crystals and chromium nitrate by the mol ratio of copper, chromium, and venus crystals and chromium nitrate powder are joined in the 10mL propionic acid successively, is stirred to dissolving fully under 60 ℃～70 ℃, and obtaining volumetric molar concentration is the precursor solution that mixes of 0.2mol/L;
B is with solution employing spin-coating method plated film on the substrate of cleaning of gained among a;
C puts into 300～600 ℃ tube furnace pre-burning with b step gained film, removes water, solvent and organism in the film, obtains inorganic thin film;
D, the inorganic thin film that step c pre-burning is obtained places tube furnace, at N 2Be warming up to 800～1000 ℃ with the speed that is not higher than 20 ℃/hour in the atmosphere, be incubated 1 hour then, furnace cooling namely gets CuCrO 2Film.
2. the Prepared by Sol Gel Method CuCrO that uses according to claim 1 2The method of film is characterized in that: among the step b, described substrate is Al 2O 3(0001) monocrystal chip.
3. the Prepared by Sol Gel Method CuCrO that uses according to claim 1 and 2 2The method of film is characterized in that: among the step c, the pre-burning time of film being put into tube furnace is 20～30 minutes.
4. the Prepared by Sol Gel Method CuCrO that uses according to claim 3 2The method of film is characterized in that: step b and c can carry out 3-5 time repeatedly.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106807391A (en) * 2017-02-28 2017-06-09 河北工业大学 A kind of CuCrO2The preparation method of powder

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105331957A (en) * 2015-10-16 2016-02-17 重庆邮电大学 Method for preparing high-conductivity CuCrO2 film through sol-gel method
CN106782876A (en) * 2016-11-24 2017-05-31 上海电机学院 The simple chemical preparation method of delafossite structure copper chromium oxygen nanometer crystal film
CN108585043B (en) * 2018-07-16 2020-10-23 广东工业大学 CuCrO2Method for producing thin film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488387A (en) * 2008-10-17 2009-07-22 中国科学院安徽光学精密机械研究所 P type doping CuCrO2 based diluted magnetic semiconductor material and preparation thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101488387A (en) * 2008-10-17 2009-07-22 中国科学院安徽光学精密机械研究所 P type doping CuCrO2 based diluted magnetic semiconductor material and preparation thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
溶胶-凝胶法制备p型透明导电CuCrO2薄膜及物性研究;王金梅;《中国科学院合肥物质科学研究院硕士学位论文》;20091231;第29-30、42页 *
王金梅.溶胶-凝胶法制备p型透明导电CuCrO2薄膜及物性研究.《中国科学院合肥物质科学研究院硕士学位论文》.2009,第29-30、42页.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106807391A (en) * 2017-02-28 2017-06-09 河北工业大学 A kind of CuCrO2The preparation method of powder

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