CN104630717A - Preparation method of P type NaXCoO2 transparent conductive thin film - Google Patents

Preparation method of P type NaXCoO2 transparent conductive thin film Download PDF

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CN104630717A
CN104630717A CN201510089089.8A CN201510089089A CN104630717A CN 104630717 A CN104630717 A CN 104630717A CN 201510089089 A CN201510089089 A CN 201510089089A CN 104630717 A CN104630717 A CN 104630717A
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transparent conductive
thin film
coo
preparation
conductive film
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CN104630717B (en
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孙丽卿
王淑芳
闫国英
傅广生
李晓苇
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Hebei University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment

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Abstract

The invention discloses a preparation method of a P type NaXCoO2 transparent conductive thin film and belongs to the technical field of functional thin film materials. The method for preparing the NaXCoO2 (x is greater than or equal to 0.5 but less than or equal to 0.8) transparent conductive thin film comprises the following steps: A, preparing a ceramic target: uniformly grinding Co3O4 powder, then carrying out compression moulding, and sintering to obtain a Co3O4 target for preparing the NaXCoO2 transparent conductive thin film by using a high temperature solid reaction process; B, carrying out pulsed laser deposition on the thin film: growing c-axis oriented CoO on a single crystal substrate by using the obtained target by virtue of a pulsed laser deposition technology to obtain a pre-prepared thin film; and C, annealing in a sodium vapor atmosphere, thereby obtaining c-axis oriented NaXCoO2 transparent conductive thin film. The NaXCoO2 transparent conductive thin film prepared by the method has high carrier concentration and relatively wide energy gap, so that the NaXCoO2 transparent conductive thin film shows good photoelectric properties such as relatively low electrical resistivity and relatively high visible light transmittance. The experimental result can be repeated, and the technical stability is good.

Description

A kind of P type Na xcoO 2the preparation method of transparent conductive film
Technical field
The invention belongs to film material with function technical field, specifically a kind of P type Na xcoO 2the preparation method of transparent conductive film.
Background technology
To defrost constructure screen wall glass from plate of flat liquid crystal display, film crystal pipe manufacturer, solar cell transparency electrode and train aircraft glass, the application of transparent conductive oxide film is very extensive.Current research mainly concentrates on ZnO, In 2o 3, SnO 2and doping system SnO 2: Sb, SnO 2: F, In 2o 3: Sn (ITO), ZnO:A1 (AZO) etc., but these materials above-mentioned all belong to N-shaped TCO material.Although prepare p-type TCO material by certain technique in the systems such as ZnO, its electroconductibility and N-shaped TCO differ greatly and the stability of preparation technology and repeatability all need to increase substantially.Therefore, prepare superior performance, stable process conditions, reproducible p-type TCO thin film material, the transparent optical electron device such as novel transparent p-n junction, transparent transistors, transparent field effect pipe that research and development make based on P type TCO design of material is had very important significance.
Summary of the invention
The present invention, in order to provide a kind of p-type TCO thin film material, devises a kind of P type Na xcoO 2the preparation method of transparent conductive film, Na prepared by present method xcoO 2transparent conductive film has high carrier concentration and wider energy gap, thus shows good photoelectric properties, and as lower resistivity and higher visible light transmissivity, experimental result can repeat, technology stability is good.
To achieve these goals, the technique means that the present invention takes is: a kind of P type Na xcoO 2the preparation method of transparent conductive film, is characterized in that: the NaxCoO of preparation 0.5≤x≤0.8 2the method steps of transparent conductive film comprises:
The preparation of A, ceramic target
By Co 3o 4after powder mull is even, compression moulding, recycling high-temperature solid phase reaction method sintering obtains preparing Na xcoO 2the Co of transparent conductive film 3o 4target;
B, pld (pulsed laser deposition)
The CoO of c-axis orientation is grown on single-crystal substrates to obtain performed thin film by pulsed laser deposition technique with the target obtained;
C, Sodium vapour atmosphere are annealed
By NaHCO 3powder covers performed thin film surface, then performed thin film is placed in high-temperature annealing furnace carries out anneal, and annealing temperature is 700-750 DEG C, the time is 1-2 hour, can obtain the Na of c-axis orientation like this xcoO 2transparent conductive film.
Described sintering carries out in high-temperature annealing furnace, and in-furnace temperature controls at 650-750 DEG C, and sintering time is 5-7 hour, and Temperature fall, to room temperature, repeats sintering 2-3 time like this.
Described Co 3o 4the purity of powder is 99.99%.
What described compression moulding adopted is hydrostatic profile method.
The laser frequency 1-10Hz of the pulsed laser deposition technique described in step B, laser energy density 1.5-3mJ/cm 2, base vacuum 10 -4-10 -5pa, oxygen pressure 1 × 10 -2-80Pa, base reservoir temperature 600-700 DEG C, substrate and target distance 40-60mm.
Single crystal substrates described in step B is the Al of c-axis orientation 2o 3, LaAlO 3, or SrTiO 3monocrystalline thin slice.
The invention has the beneficial effects as follows: one, technology stability is good, sample repetition rate is high; They are two, the p-type Na of preparation years old xcoO 2transparent conductive film crystalline quality is good, along c-axis direction oriented growth and not containing any dephasign; They are three, the p-type Na of preparation years old xcoO 2transparent conductive film has higher specific conductivity and visible light transmissivity, and photoelectricity quality factor is high.
Accompanying drawing explanation
Fig. 1 is to obtained Na xcoO 2the XRD figure spectrum that transparent conductive film obtains after using the test of D8 type x-ray diffractometer.
Fig. 2 is Na xcoO 2the transmitted spectrum of transparent conductive film, in figure, X-coordinate is wavelength, and ordinate zou is transmitance.
Fig. 3 is Na xcoO 2the low-temperature resistivity collection of illustrative plates of transparent conductive film, in figure, X-coordinate is temperature, and ordinate zou is resistivity.
Fig. 4 is by Na of the present invention xcoO 2the uptake factor of transparent conductive film carries out the optical band gap that matching obtains, and in figure, X-coordinate is photon energy (h υ), and ordinate zou is (α h υ) 2.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
Embodiment one, for x=0.7, p-type Na 0.7coO 2the preparation method of transparent conductive film carries out according to following steps order:
A, by purity be 99.99% high-purity Co 3o 4after powder mull is even, use static pressure method compression moulding, presintering 6 hours in the high-temperature annealing furnace of 700 DEG C, Temperature fall, to room temperature, repeats sintering 2 times like this, the Co that obtained deposition is used 3o 4target;
B, the Co that will obtain 3o 4target puts into PLD cavity, by pulsed laser deposition, at Al 2o 3substrate is according to above-mentioned parameter deposition CoO film;
C, anneal under Sodium vapour atmosphere, concrete annealing process is:
By NaHCO 3powder covers performed thin film surface, will be coated with NaHCO 3performed thin film be placed in high-temperature annealing furnace and carry out anneal 2 hours, annealing temperature 750 DEG C, obtains the Na along c-axis oriented growth 0.7coO 2transparent conductive film.
Be the XeCl quasi-molecule laser of 308nm with laser apparatus, XRD test shows the p-type Na prepared 0.7coO 2film is c-axis oriented growth, can see accompanying drawing 1; Its room temperature resistivity is 1.2m Ω cm, can see accompanying drawing 2; Visible ray average transmittances is 37%, can see accompanying drawing 3; Optical band gap is 2.61eV, can see accompanying drawing 4.
Embodiment two, for x=0.5, p-type Na 0.5coO 2the preparation method of transparent conductive film carries out according to following steps order:
A, by purity be 99.99% high-purity Co 3o 4after powder mull is even, use static pressure method compression moulding, presintering 5 hours in the high-temperature annealing furnace of 750 DEG C, Temperature fall, to room temperature, repeats sintering 3 times like this, the Co that obtained deposition is used 3o 4target;
B, the Co that will obtain 3o 4target puts into PLD cavity, by pulsed laser deposition, at LaAlO 3substrate is according to above-mentioned parameter deposition CoO film;
C, anneal under Sodium vapour atmosphere, concrete annealing process is:
By NaHCO 3powder covers performed thin film surface, will be coated with NaHCO 3performed thin film be placed in high-temperature annealing furnace and carry out anneal 2 hours, annealing temperature 700 DEG C, obtains the Na along c-axis oriented growth 0.7coO 2transparent conductive film.
Be the XeCl quasi-molecule laser of 308nm with laser apparatus, XRD test shows the p-type Na prepared 0.5coO 2film is c-axis oriented growth, and its room temperature resistivity is 1.21m Ω cm; Visible ray average transmittances is 37%; Optical band gap is 2.63eV.
Embodiment three, for x=0.8, p-type transparent conductive film Na 0.8coO 2preparation method carry out according to following steps order:
A, by purity be 99.99% high-purity Co 3o 4after powder mull is even, use static pressure method compression moulding, presintering 7 hours in the high-temperature annealing furnace of 650 DEG C, Temperature fall, to room temperature, repeats sintering 3 times like this, the Co that obtained deposition is used 3o 4target;
B, the Co that will obtain 3o 4target puts into PLD cavity, by pulsed laser deposition, at SrTiO 3substrate is according to above-mentioned parameter deposition CoO film;
C, anneal under Sodium vapour atmosphere, concrete annealing process is:
By NaHCO 3powder covers performed thin film surface, will be coated with NaHCO 3performed thin film be placed in high-temperature annealing furnace and carry out anneal 1 hour, annealing temperature 750 DEG C, obtains the Na along c-axis oriented growth 0.8coO 2transparent film.
Be the XeCl quasi-molecule laser of 308nm with laser apparatus, XRD test shows the p-type Na prepared 0.8coO 2film is c-axis oriented growth; Its room temperature resistivity is 1.2m Ω cm; Visible ray average transmittances is 37.2%; Optical band gap is 2.62eV.

Claims (6)

1. a P type Na xcoO 2the preparation method of transparent conductive film, is characterized in that: the Na of preparation 0.5≤x≤0.8 xcoO 2the method steps of transparent conductive film comprises:
The preparation of A, ceramic target
By Co 3o 4after powder mull is even, compression moulding, recycling high-temperature solid phase reaction method sintering obtains preparing Na xcoO 2the Co of transparent conductive film 3o 4target;
B, pld (pulsed laser deposition)
The CoO of c-axis orientation is grown on single-crystal substrates to obtain performed thin film by pulsed laser deposition technique with the target obtained;
C, Sodium vapour atmosphere are annealed
By NaHCO 3powder covers performed thin film surface, then performed thin film is placed in high-temperature annealing furnace carries out anneal, and annealing temperature is 700-750 DEG C, the time is 1-2 hour, can obtain the Na of c-axis orientation like this xcoO 2transparent conductive film.
2. a kind of P type Na according to claim 1 xcoO 2the preparation method of transparent conductive film, is characterized in that: described sintering carries out in high-temperature annealing furnace, and in-furnace temperature controls at 650-750 DEG C, and sintering time is 5-7 hour, and Temperature fall, to room temperature, repeats sintering 2-3 time like this.
3. a kind of P type Na according to claim 1 xcoO 2the preparation method of transparent conductive film, is characterized in that: described Co 3o 4the purity of powder is 99.99%.
4. a kind of P type Na according to claim 1 xcoO 2the preparation method of transparent conductive film, is characterized in that: what described compression moulding adopted is hydrostatic profile method.
5. a kind of P type Na according to claim 1 xcoO 2the preparation method of transparent conductive film, is characterized in that: the laser frequency 1-10Hz of the pulsed laser deposition technique described in step B, laser energy density 1.5-3mJ/cm 2, base vacuum 10 -4-10 -5pa, oxygen pressure 1 × 10 -2-80Pa, base reservoir temperature 600-700 DEG C, substrate and target distance 40-60mm.
6. a kind of P type Na according to claim 1 xcoO 2the preparation method of transparent conductive film, is characterized in that: the single crystal substrates described in step B is the Al of c-axis orientation 2o 3, LaAlO 3, or SrTiO 3monocrystalline thin slice.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107827165A (en) * 2017-10-20 2018-03-23 三峡大学 A kind of sodium cobalt/cobalt oxide sodium-ion battery positive material and preparation method thereof
CN109095514A (en) * 2018-09-11 2018-12-28 安徽工业大学 One kind preparing different-shape P2-Na with template0.7CoO2The method of material
CN109775764A (en) * 2019-01-10 2019-05-21 三峡大学 A kind of spherical NaxCoO2Sodium-ion battery positive material and preparation method thereof

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CN103936425A (en) * 2014-01-20 2014-07-23 清华大学 Preparation method of ceramic plate

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CN103936425A (en) * 2014-01-20 2014-07-23 清华大学 Preparation method of ceramic plate

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H. ZHOU等: ""Fabrication of NaxCoO2 thin films by pulsed laser deposition"", 《THIN SOLID FILMS》 *
HIROMICHI OHTA 等: ""Recent Progress in Oxide Thermoelectric Materials: p-Type Ca3Co4O9 and n-Type SrTiO3-"", 《INORGANIC CHEMISTRY》 *
HIROMICHI OHTA等: ""Reactive Solid-Phase Epitaxial Growth of NaxCoO2 (x∼0.83) via Lateral Diffusion of Na into a Cobalt Oxide Epitaxial Layer"", 《CRYSTAL GROWTH & DESIGN》 *
SHUFANG WANG等: ""Laser-induced voltage effects in c-axis inclined NaxCoO2 thin films"", 《APPLIED SURFACE SCIENCE》 *
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107827165A (en) * 2017-10-20 2018-03-23 三峡大学 A kind of sodium cobalt/cobalt oxide sodium-ion battery positive material and preparation method thereof
CN107827165B (en) * 2017-10-20 2019-04-30 三峡大学 A kind of sodium cobalt/cobalt oxide sodium-ion battery positive material and preparation method thereof
CN109095514A (en) * 2018-09-11 2018-12-28 安徽工业大学 One kind preparing different-shape P2-Na with template0.7CoO2The method of material
CN109775764A (en) * 2019-01-10 2019-05-21 三峡大学 A kind of spherical NaxCoO2Sodium-ion battery positive material and preparation method thereof

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