CN101215702A - Method for preparing transparent conductive oxide thin film with P-type delafossite structure - Google Patents
Method for preparing transparent conductive oxide thin film with P-type delafossite structure Download PDFInfo
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- CN101215702A CN101215702A CNA2007101920504A CN200710192050A CN101215702A CN 101215702 A CN101215702 A CN 101215702A CN A2007101920504 A CNA2007101920504 A CN A2007101920504A CN 200710192050 A CN200710192050 A CN 200710192050A CN 101215702 A CN101215702 A CN 101215702A
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- oxide
- film
- delafossite structure
- transparent conductive
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Abstract
The invention discloses a method for preparing a P-type delafossite structure transparent conductive oxide film, first cuprous oxide, chromium oxide and oxide of metal M are weighted according to the molar ratio of cuprum, chromium and M, which is 1: (0.75-1) : (0-0.25), after being mixed, raw materials are milled, then power which is milled is compacted to be prepared into compound target, which is prepared in normal temperature and is not sintered in high temperature, and the cuprous oxide, the cuprous oxide and the oxide of the metal M do not produce a chemical reaction. The obtained target is deposited on a base plate with a CuCr1-xMxO2 film through pulsed laser deposition, and the x is equal or greater than 0 and is equal or lesser than 0.25. The prepared delafossite structure polycystic CuCr1-xMxO2 film (0<=x<=0.25) has high conductivity and visible light transmittance, and laboratory results have reproducibility.
Description
Technical field
The present invention relates to a kind of delafossite structure p type transparent conductive oxide (Transparent ConductingOxide, TCO) preparation of film, especially CuCr
1-xM
xO
2Pulsed laser deposition (Pulsed Laser Deposition, PLD) preparation method of (0≤x≤0.25, M is metallic cation Mg, Ca, Ni etc.) film.
Background technology
To low radiating building glass coating, the application of transparent conductive oxide film is very extensive from the transparency electrode of flat-panel monitor.The more TCO material of research comprises ZnO, In at present
1-xSn
xO
3(ITO), SnO
2: F, Cd
2SnO
4Deng, wherein ITO and SnO
2Development is comparatively ripe, but they are n-TCO.Though can be in systems such as ZnO by certain prepared p-TCO film, its complex process and stability await further to improve.Prepare the p-TCO thin-film material of superior performance, process stabilizing and itself and n-TCO film are carried out compound, have very important significance studying transparent optical electronics devices such as transparent pn knot, transparent transistors, transparent field effect pipe.Sato reported p N-type semiconductorN NiO film for the first time in 1993, and it has 40% transmitance in visible-range.But because its lower visible light transmissivity, NiO does not cause extensive concern.Up to 1997, people such as Kawazoe reported delafossite structure oxide compound CuAlO
2Film is the p-TCO material, and has electricity and optical property preferably, has evoked the research interest of people to p-TCO again.
The chemical formula of delafossite structure oxide compound can be written as ABO
2, wherein A is monovalent metallic ions such as Cu, Ag, B is trivalent ions such as Al, La, Sc, In, Cr.Because the difference of atomic arrangement mode, the delafossite structure oxide compound has two kinds of different crystalline networks, therefore has 2H and two kinds of crystalline phases of 3R.In the delafossite system, CuCrO
2Specific conductivity be about 1Scm
-1, and mix 5% Mg in the Cr position, specific conductivity rises to 220Scm
-1, this is a specific conductivity maximum among the p-TCO that reports at present.
The preparation method of delafossite structure sull has chemical solution method, chemical Vapor deposition process and sputtering method, wherein the PLD method has and is easy to accurately reproduce the target composition, the advantage of growing epitaxial single crystal film and multilayer film is present the most frequently used delafossite structure sull preparation method.Use the PLD thin films to prepare target in advance, in traditional method, adopt high-temperature solid phase reaction method to prepare CuCrO
2Target need long-time sintering be to guarantee abundant reaction down at comparatively high temps (～1100 ℃), and energy loss is very big.Now energy problem is more and more severeer, uses more method for saving energy to prepare high-quality p-TCO film and will have important Research Significance.
Summary of the invention
It is simple to the objective of the invention is to propose a kind of technology, and energy consumption is low, can prepare have higher specific conductivity, the preparation method of transmission of visible light p type delafossite structure transparent conductive oxide film.
The preparation method that the present invention proposes is as follows:
The preparation method of p type delafossite structure transparent conductive oxide film is characterized in that finishing according to the following steps:
(a) mol ratio by copper, chromium and M is 1: (0.75～1): (0～0.25), and the oxide compound of weighing Red copper oxide, chromic oxide and metal M mixes the back ball milling with raw material;
(b) with the powder compact after the ball milling, be prepared into composite target material, target is that normal temperature prepares without high temperature sintering, and chemical reaction does not take place the oxide compound of Red copper oxide and chromic oxide and M;
(c) on substrate, deposit CuCr with the target that obtains by pulsed laser deposition
1-xM
xO
2Film, 0≤x≤0.25.
The preparation method of described p type delafossite structure transparent conductive oxide film is characterized in that described M refers to Mg, Ca, Ni element.
The preparation method of described p type delafossite structure transparent conductive oxide film is characterized in that described deposition CuCr
1-xM
xO
2The technical qualification of film are: laser frequency 1-20HZ, laser energy density 1-10J/cm
2, base vacuum 10
-3-10
-6Pa, oxygen presses 1 * 10
-2～30Pa, substrate temperature 400-1000K, the distance 20～70mm of substrate and target.
The preparation method of described p type delafossite structure transparent conductive oxide film is characterized in that used substrate is Al
2O
3(0 0 /), quartz or Si sheet.
Beneficial effect with respect to prior art is, one, and the preparation technology of target is simple, need not to carry out high temperature sintering, makes production cost be reduced significantly, makes it be easy to large-scale industrial production, is beneficial to the commercial applications of its product; Its two, the film that makes is the CuCr of delafossite structure
1-xM
xO
2(0≤x≤0.25) polycrystalline phase becomes mutually even, and does not contain dephasign; Its three, the delafossite structure polycrystalline CuCr that makes
1-xM
xO
2(0≤x≤0.25) film has higher specific conductivity and visible light transmissivity, and experimental result possesses and can repeat.
Description of drawings
Fig. 1 is the delafossite structure CuCr to making
1-xM
xO
2(0≤x≤0.25) film uses the XRD figure spectrum that obtains after the test of Phillips X ' Pert type X-ray diffraction (XRD) instrument, and the X-coordinate among the figure is that diffraction angle, ordinate zou are relative intensity.By the position of each diffraction peak in the XRD figure and relative intensity as can be known, this polycrystalline material is the 2H-CuCrO of delafossite structure
2The polycrystalline phase;
Fig. 2 is delafossite structure CuCr
1-xM
xO
2(0≤x≤0.25) film transmitted spectrum, the X-coordinate among the figure is a wavelength, ordinate zou is a transmitance.
Fig. 3 is by to delafossite structure CuCr
1-xM
xO
2The uptake factor of (0≤x≤0.25) film fits the optical bandwidth that obtains, and the X-coordinate among the figure is that photon energy (hv), ordinate zou are (α hv)
2
Embodiment
At first make or buy Red copper oxide, chromium sesquioxide, the oxide compound of M, Al from market with ordinary method
2O
3Single crystal substrate, high purity oxygen gas, then,
Embodiment 1: finish preparation according to the following steps order:
(a) mol ratio by copper and chromium is 1: 1, behind weighing Red copper oxide and the chromic oxide, places ball grinder to grind on planetary ball mill its mixing, and wherein, ratio of grinding media to material is 25: 1, and the rotating speed of ball milling is 200rpm, and the time is 10 hours.
(b) powder behind the ball milling is placed the mould of desired shape carry out the single shaft press forming, make the used target of deposition.
(c) target that makes is put into deposit cavity, by pulsed laser deposition, at Al
2O
3Deposit CuCrO according to the parameter shown in the table 1 on the substrate
2Film.Thereby make as Fig. 1 and the blocky delafossite structure CuCrO shown in Fig. 2, Fig. 3, middle curve
2Film.
Among Fig. 3, can draw by fitting, film is a direct band-gap semicondictor, and optical bandwidth is 3.23eV.
Embodiment 2: finish preparation according to the following steps order:
(a) mol ratio by copper, chromium and magnesium is 1: (1-0.95): (0-0.05), behind weighing Red copper oxide, chromic oxide and the magnesium oxide, place ball grinder on planetary ball mill, to grind its mixing,
Wherein, ratio of grinding media to material is 20: 1, and the rotating speed of ball milling is that 450rpm, time are 25 hours.
(b) powder behind the ball milling is placed the mould of desired shape carry out the single shaft press forming, make the used target of deposition.
(c) target that makes is put into deposit cavity, by pulsed laser deposition, at Al
2O
3Deposit according to the parameter shown in the table 1 on the substrate, thereby make delafossite structure CuCr
1-xMg
xO
2(0≤x≤0.05) film.
Embodiment 3: finish preparation according to the following steps order:
(a) mol ratio by copper, chromium and calcium is 1: (1～0.97): (0～0.03), behind weighing Red copper oxide, chromic oxide and the calcium oxide, place ball grinder on planetary ball mill, to grind its mixing, wherein, ratio of grinding media to material is 30: 1, and the rotating speed of ball milling is that 400rpm, time are 15 hours.
(b) powder behind the ball milling is placed the mould of desired shape carry out the single shaft press forming, make the used target of deposition.
(c) target that makes is put into deposit cavity, by pulsed laser deposition, at Al
2O
3Deposit according to the parameter shown in the table 1 on the substrate, thereby make delafossite structure CuCr
1-xCa
xO
2(0≤x≤0.03) film.
Embodiment 4: finish preparation according to the following steps order:
(a) mol ratio by copper, chromium and nickel is 1: (1～0.90): (0～0.10), behind weighing Red copper oxide, chromium sesquioxide and the nickel sesquioxide, place ball grinder on planetary ball mill, to grind its mixing, wherein, ratio of grinding media to material is 40: 1, and the rotating speed of ball milling is that 300rpm, time are 20 hours.
(b) powder behind the ball milling is placed the mould of desired shape carry out the single shaft press forming, make the used target of deposition.
(c) target that makes is put into deposit cavity, by pulsed laser deposition, at Al
2O
3Deposit according to the parameter shown in the table 1 on the substrate, thereby make delafossite structure CuCr
1-xNi
xO
2(0≤x≤0.10) film.
Obviously, those skilled in the art can be to the CuCr of delafossite structure of the present invention
1-xM
xO
2(0≤x≤0.25, M is metallic cation Mg, Ca, the Ni etc.) preparation method of film and the material of preparation thereof carry out various changes and modification and do 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.
Claims (4)
1.p the preparation method of type delafossite structure transparent conductive oxide film is characterized in that finishing according to the following steps:
(a) mol ratio by copper, chromium and M is 1: (0.75～1): (0～0.25), and the oxide compound of weighing Red copper oxide, chromic oxide and metal M mixes the back ball milling with raw material;
(b) with the powder compact after the ball milling, be prepared into composite target material, target is that normal temperature prepares without high temperature sintering, and chemical reaction does not take place the oxide compound of Red copper oxide and chromic oxide and M;
(c) on substrate, deposit CuCr with the target that obtains by pulsed laser deposition
1-xM
xO
2Film, 0≤x≤0.25.
2. the preparation method of p type delafossite structure transparent conductive oxide film according to claim 1 is characterized in that described M refers to Mg, Ca, Ni element.
3. the preparation method of p type delafossite structure transparent conductive oxide film according to claim 1 is characterized in that described deposition CuCr
1-xM
xO
2The technical qualification of film are: laser frequency 1-20HZ, laser energy density 1-10J/cm
2, base vacuum 10
-3-10
-6Pa, oxygen presses 1 * 10
-2～30Pa, substrate temperature 400-1000K, the distance 20～70mm of substrate and target.
4. the preparation method of p type delafossite structure transparent conductive oxide film according to claim 1 is characterized in that used substrate is Al
2O
3(0 0 /), quartz or Si sheet.
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|---|---|---|---|
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|---|---|---|---|
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| CN100560799C CN100560799C (en) | 2009-11-18 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010021921A1 (en) | 2010-05-28 | 2011-12-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Sol and method for producing a crystalline mixed oxide layer, substrate with mixed oxide layer and use thereof |
| CN106006738A (en) * | 2016-05-26 | 2016-10-12 | 华北水利水电大学 | Ni-doped CuCrO2-based oxide thermoelectric material and preparation method thereof |
| CN107988629A (en) * | 2017-11-30 | 2018-05-04 | 山东大学 | A kind of preparation method of low resistivity p-type cuprous oxide epitaxial film |
| CN108022694A (en) * | 2017-12-04 | 2018-05-11 | 中国科学院合肥物质科学研究院 | A kind of preparation method of transparent conductive oxide film-nanometer line network |
| CN112310287A (en) * | 2020-10-15 | 2021-02-02 | 上海工程技术大学 | Preparation method of high-stability inorganic hole transport film capable of being produced in large scale |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7608308B2 (en) * | 2006-04-17 | 2009-10-27 | Imra America, Inc. | P-type semiconductor zinc oxide films process for preparation thereof, and pulsed laser deposition method using transparent substrates |
-
2007
- 2007-12-27 CN CNB2007101920504A patent/CN100560799C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102010021921A1 (en) | 2010-05-28 | 2011-12-01 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Sol and method for producing a crystalline mixed oxide layer, substrate with mixed oxide layer and use thereof |
| CN106006738A (en) * | 2016-05-26 | 2016-10-12 | 华北水利水电大学 | Ni-doped CuCrO2-based oxide thermoelectric material and preparation method thereof |
| CN107988629A (en) * | 2017-11-30 | 2018-05-04 | 山东大学 | A kind of preparation method of low resistivity p-type cuprous oxide epitaxial film |
| CN108022694A (en) * | 2017-12-04 | 2018-05-11 | 中国科学院合肥物质科学研究院 | A kind of preparation method of transparent conductive oxide film-nanometer line network |
| CN108022694B (en) * | 2017-12-04 | 2019-07-09 | 中国科学院合肥物质科学研究院 | A kind of preparation method of transparent conductive oxide film-nanometer line network |
| CN112310287A (en) * | 2020-10-15 | 2021-02-02 | 上海工程技术大学 | Preparation method of high-stability inorganic hole transport film capable of being produced in large scale |
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|---|---|
| CN100560799C (en) | 2009-11-18 |
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