CN102560362A - Method for preparing p-type CuAlO2 transparent conductive film - Google Patents
Method for preparing p-type CuAlO2 transparent conductive film Download PDFInfo
- Publication number
- CN102560362A CN102560362A CN2012100591500A CN201210059150A CN102560362A CN 102560362 A CN102560362 A CN 102560362A CN 2012100591500 A CN2012100591500 A CN 2012100591500A CN 201210059150 A CN201210059150 A CN 201210059150A CN 102560362 A CN102560362 A CN 102560362A
- Authority
- CN
- China
- Prior art keywords
- cualo
- conductive film
- transparent conductive
- type
- electron beam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention relates to a method for preparing a p-type CuAlO2 transparent conductive film. The method comprises the following steps of: performing artificial grinding or mechanical ball milling on Cu2O and Al2O3 which serve as raw materials, mixing uniformly, putting the mixed powder into a powder tablet machine to form a cylindrical target blank, putting the target blank into a corundum crucible, covering, putting into a single crystal furnace, and sintering at the temperature of between 1,100 DEG C and 1,200 DEG C for 10 to 12 hours to obtain a CuAlO2 ceramic target material; and putting the sintered CuAlO2 target material into a crucible of electron beam evaporation coating equipment, vacuumizing until the background is vacuum, performing electron beam evaporation coating under the condition that any reactant gas is not introduced, and controlling electron beams and deposition time to obtain the p-type CuAlO2 transparent conductive film. The p-type CuAlO2 transparent conductive film is easy to prepare, high in purity and clean and environment-friendly in the preparation process, and is heated uniformly in the sintering process.
Description
Technical field
The invention belongs to the semiconductor material preparing technical field, be specifically related to a kind of preparation p type CuAlO
2The method of transparent conductive film.
Background technology
Transparent conductive oxide (TCO) is an indispensable material in the fields such as flat-panel monitor, solar cell, opto-electronic device, like In
2O
3: Sn (ITO), ZnO:Al (AZO), and SnO
2: F (FTO) etc.; They are n type electro-conductive material; Its film only uses as single electricity or optical coating, and the pn knot is the basis of semiconducter device, and p type TCO material is a requisite material of making transparent pn knot; But p type TCO development is comparatively slow, has restricted the development and application of semi-conductor related device.
People's reported first such as Kawazoe in 1997 have a CuAlO of p type delafossite structure
2Transparent conductive oxide film has caused the research and development enthusiasm of people to p type transparent conductive film, but CuAlO so far
2The performance of film still awaits improving.Present CuAlO
2Film mainly is to adopt pulsed laser deposition equipment to make, and the uniformity of film that this method makes is poor, the preparation complex equipments, and cost is too high, is difficult to realize p type CuAlO
2Application and the popularization of film in industry.Although the film of magnetically controlled sputter method preparation has the even film forming of big area, is easy to industrialized advantage; But its prepared film crystallinity is poor; And be difficult to keep the consistence of thin film composition and target, be not suitable for preparing film with multielement stoichiometric ratio.Therefore, exploitation high quality p type CuAlO
2The low cost of film, high-level efficiency preparation have important use and are worth.
The electron beam evaporation deposition technology has advantage simple to operation; And its preparation has characteristics such as beam energy height, vaporator rate be fast in thin-film process; Preparation for sull; Can not feed any reactant gases, from ceramic target evaporation film forming on substrate, be the method and the production technique of a kind of low cost, high-level efficiency deposition oxide film directly.The purified CuAlO that is suitable for the use of electron beam evaporation deposition equipment of synthetic crystalline phase
2Ceramic target is very crucial to quality of forming film.Usually the source material (being target) of electron beam evaporation deposition equipment is to be placed on a rotary bore to be about in 3.6cm copper crucible or the carbon crucible; Utilizing the magnetic field controlling electron beam to reach evaporation film forming on substrate on the source material, is a kind of consistent film coating method of composition that can keep target and film cheaply.The preparation of target can not be too big or too thick, otherwise, the difficult additional process that increases that is shaped during compressing tablet, the inequality that when sintering, is prone to be heated in addition causes the target crystalline phase impure, and is difficult for putting into the source crucible.CuAlO
2Target is temperature required 1000 in the preparation process
oMore than the C, by starting material Cu
2O and Al
2O
3The generation solid state reaction makes, synthetic CuAlO
2Required starting material Cu
2O and Al
2O
3Have advantages such as cheap, environmental protection.
Goal of the invention
The objective of the invention is to propose a kind of simple, cost is low, efficient is high preparation p type CuAlO
2The method of transparent conductive film.
The inventive method is specially: at first, adopt Cu
2O and Al
2O
3Be raw material; Process underhand polish or mechanical ball milling are more than 4 hours; Make it to mix, the mixed powder tabletting machine of packing into was kept 1～3 minute under the pressure of 30～50 MPa, processing diameter is that 1.4 cm, thickness are the cylindric target blank of 2.1 mm; Target blank is put into corundum crucible build and be placed on single crystal growing furnace, controlled temperature is 1100
oC～1200
oThe C sintering promptly obtained CuAlO in 10～15 hours
2Ceramic target; Then, with the CuAlO that bakes
2Ceramic target is put into the copper crucible or the carbon crucible of electron beam evaporation deposition equipment, is evacuated to 1 * 10
-4Below the Pa, under the condition that does not feed any reactant gases, carry out electron beam evaporation deposition, controlling electron beam stream is 20mA～250mA, and evaporation time is 5～45 minutes, promptly obtains p type CuAlO
2Transparent conductive film.
Beneficial effect of the present invention:
The target that the present invention is prepared is because volume is little; Be heated in the sintering process evenly, the purified target of the crystalline phase that is easy to get is easy to the crucible bottom of overlay electronic beam evaporation filming equipment simultaneously; Be unlikely by the electron beam puncture, be applicable to the fixing vacuum coating system that requires of target shape is used.
The present invention uses single crystal growing furnace to carry out once many target sintering in batches, and need not double sintering, promptly gets the good target of crystallization.
Do not feed any working gas during electron beam evaporation deposition, reduced complicated gas path pipe facility, background pressure is 1 * 10
-4Pa, process of the test is simple.
During electron beam evaporation deposition, the vapor deposition condition is: the vapor deposition high pressure is 6 kV or 8kV gear, and electronic beam current is 20～250mA, 5～45 minutes vapor deposition time.
Among the present invention, the transparency of prepared film can be controlled improvement through controlling electron beam stream, substrate temperature and vapor deposition time.
Description of drawings
Fig. 1 is the CuAlO of embodiment 1 preparation
2The X-ray diffractogram of ceramic target.
Fig. 2 is the CuAlO of embodiment 1 preparation
2The ceramic target digital photograph.
Fig. 3 is the CuAlO of embodiment 1 preparation
2Target SEM figure.
Fig. 4 is the CuAlO of embodiment 2 preparations
2Target places the digital photograph of electron beam evaporation copper crucible.
Fig. 5 is the CuAlO of electron beam evaporation deposition preparation among the embodiment 2
2The SEM figure of film.
Fig. 6 is the CuAlO of electron beam evaporation deposition preparation under the different condition
2The digital photograph of film.
Fig. 7 is the CuAlO of electron beam evaporation deposition preparation under the different condition
2The transmittance graph figure of film.
Embodiment
Further describe the present invention through specific embodiment below:
Embodiment 1, preparation CuAlO
2Ceramic target: with purity is the Cu more than 99.99%
2O and Al
2O
3Mixed powder process underhand polish or mechanical ball milling are more than 4 hours; Make grain diameter reach 300～500 nm scopes, and uniform mixing, mixed powder is packed in the powder compressing machine hopper; Under the pressure of 40 MPa, kept 3 minutes; Process the cylindric target blank that diameter and thickness are respectively 1.4 cm and 2.1mm, target blank is put into corundum crucible build and be placed on single crystal growing furnace, controlled temperature is 1150
oC sintering 12 hours, temperature rise rate are 5
oC/min after the completion to be sintered, is cooled to 80 naturally
oTake out below the C, promptly obtain CuAlO
2Ceramic target, target diameter are 1.3 cm, and thickness is 2 mm, are p type conduction target through the thermal probe test, and the resistance value of measuring the 1cm distance with volt ohm-milliammeter is about 80 k Ω.Like Fig. 1 is the X-ray diffractogram of prepared target, and Fig. 2 is the digital photograph of target, and Fig. 3 is the SEM figure of target.
Embodiment 2, adopt with embodiment 1 same method to prepare CuAlO
2Ceramic target.Substrate is common slide glass, successively cleans in each 15 minutes through pure water, alcohol and acetone UW.Electron beam evaporation prepares CuAlO
2Film: with the CuAlO that bakes
2Target is put into the copper crucible of electron beam evaporation deposition equipment, and is as shown in Figure 4, is advisable to be full of 2/3rds of crucible, is evacuated to 5 * 10 then
-5Pa under the condition that does not feed any reactant gases, is a substrate with the simple glass; Carry out electron beam evaporation deposition, the electron beam evaporation high pressure is 6 kV gears, and sweep current X is 0.6 mA; Y is 0 mA, and the scanning fluctuation range is positive and negative 0.05 mA, and controlling electron beam stream is 30 mA; Be evaporated to 15 minutes time, promptly obtain p type CuAlO
2Transparent conductive film is the SEM figure of film like Fig. 5.
Embodiment 3, adopt with embodiment 1 same method to prepare CuAlO
2Ceramic target.Substrate is common slide glass, successively cleans in each 15 minutes through pure water, alcohol and acetone UW.Electron beam evaporation prepares CuAlO
2Film: with the CuAlO that bakes
2Target is put into the copper crucible of electron beam evaporation deposition equipment, is evacuated to 1 * 10
-4Pa under the condition that does not feed any reactant gases, is a substrate with the simple glass; Carry out electron beam evaporation deposition, the electron beam evaporation high pressure is 6 kV gears, and sweep current X is 0.6 mA; Y is 0 mA, and the scanning fluctuation range is positive and negative 0.05 mA, and controlling electron beam stream is 30 mA; Be evaporated to 5 minutes time, promptly obtain p type CuAlO
2Transparent conductive film is the digital photograph of corresponding film under this condition like Far Left sample among Fig. 6, and the top curve is the transmittance graph figure of corresponding film among Fig. 7.
Embodiment 4, adopt with embodiment 1 same method to prepare CuAlO
2Ceramic target.Substrate is common slide glass, successively cleans in each 15 minutes through pure water, alcohol and acetone UW.Electron beam evaporation prepares CuAlO
2Film: with the CuAlO that bakes
2Target is put into the copper crucible of electron beam evaporation deposition equipment, is evacuated to 1 * 10
-4Pa under the condition that does not feed any reactant gases, is a substrate with the simple glass; Carry out electron beam evaporation deposition, the electron beam evaporation high pressure is 6 kV gears, and sweep current X is 0.6 mA; Y is 0 mA, and the scanning fluctuation range is positive and negative 0.05 mA, and controlling electron beam stream is 30 mA; Be evaporated to 35 minutes time, promptly obtain p type CuAlO
2Transparent conductive film, like Fig. 6 middle sample, the digital photograph of corresponding film under the condition for this reason, Fig. 7 intermediate curve is the transmittance graph figure of corresponding film.
Embodiment 5, adopt with embodiment 1 same method to prepare CuAlO
2Ceramic target.Substrate is common slide glass, successively cleans in each 15 minutes through pure water, alcohol and acetone UW.Electron beam evaporation prepares CuAlO
2Film: with the CuAlO that bakes
2Target is put into the copper crucible of electron beam evaporation deposition equipment, is evacuated to 1 * 10
-4Pa under the condition that does not feed any reactant gases, is a substrate with the simple glass; Carry out electron beam evaporation deposition, the electron beam evaporation high pressure is 6 kV gears, and sweep current X is 0.6 mA; Y is 0 mA, and the scanning fluctuation range is positive and negative 0.05 mA, and controlling electron beam stream is 80 mA; Be evaporated to 35 minutes time, promptly obtain p type CuAlO
2Transparent conductive film, like Fig. 6 rightmost sample, the digital photograph of corresponding film under the condition for this reason, the bottom curve of Fig. 7 is the transmittance graph figure of corresponding film.
Test-results shows, the p type CuAlO of the present invention's preparation
2Advantages such as target has that material environment friendly is pollution-free, the preparation process is simple to operation, target good conductivity, crystalline phase are pure are fit to vacuum coating system and carry out high quality p type CuAlO as target
2Depositing of thin film.The present invention adopts electron beam evaporation deposition equipment to prepare p type CuAlO
2Film has the advantages that the process of the test time is short, efficient is high, and the present invention reaches 1 * 10 owing in the electron beam evaporation plating process, do not feed any gas at the base vacuum degree
-4Can directly open line during Pa and carry out vapor deposition; Plated film speed is high, and the film of preparation is even, and is simple to operate; Be a kind of method for preparing high quality p type transparent conductive oxide film, the p type film that is obtained has the potential using value in semi-conductor transparent electronics field.
Claims (7)
1. one kind prepares p type CuAlO
2The method of transparent conductive film is characterized in that this method may further comprise the steps: at first, adopt Cu
2O and Al
2O
3Be raw material; Process underhand polish or mechanical ball milling are more than 4 hours; Make it to mix, the mixed powder tabletting machine of packing into was kept 1～3 minute under the pressure of 30～50 MPa, processing diameter is that 1.4 cm, thickness are the cylindric target blank of 2.1 mm; Target blank is put into corundum crucible build and be placed on single crystal growing furnace, controlled temperature is 1100
oC～1200
oThe C sintering promptly obtained CuAlO in 10～15 hours
2Ceramic target; Then, with the CuAlO that bakes
2Ceramic target is put into the copper crucible or the carbon crucible of electron beam evaporation deposition equipment, is evacuated to 1 * 10
-4Below the Pa, under the condition that does not feed any reactant gases, carry out electron beam evaporation deposition, controlling electron beam stream is 20mA～250mA, and evaporation time is 5～45 minutes, promptly obtains p type CuAlO
2Transparent conductive film.
2. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: Cu
2O and Al
2O
3Purity should be more than 99.99%, grain diameter is 300～500 nm after grinding.
3. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: it is 1.3 cm that cylindric target blank sintering is processed the ceramic target diameter, and thickness is 2 mm.
4. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: sintering in single crystal growing furnace, temperature are 1150
oC, the time is 12 hours, temperature rise rate is 5
oC/min after the completion to be sintered, is cooled to 80 naturally
oTake out below the C.
5. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: p type conductive film CuAlO
2Simple preparation fast, make by electron beam evaporation deposition equipment, with the CuAlO that bakes
2Ceramic target is put into the copper crucible or the carbon crucible of electron beam evaporation deposition equipment, is advisable to be full of 2/3rds of crucible, and base vacuum is evacuated to 1 * 10
-4Carry out thin film deposition below the Pa.
6. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: p type CuAlO
2The thickness of conductive film can be regulated through controlling electron beam stream size and depositing time.
7. preparation p type CuAlO according to claim 1
2The method of transparent conductive film is characterized in that: when carrying out electron beam evaporation deposition, be the simple glass slide glass with the substrate, and prepared p type CuAlO
2Conductive film have certain transparency, through regulating preparation parameter its transsmissivity is reached more than 70%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100591500A CN102560362A (en) | 2012-03-08 | 2012-03-08 | Method for preparing p-type CuAlO2 transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100591500A CN102560362A (en) | 2012-03-08 | 2012-03-08 | Method for preparing p-type CuAlO2 transparent conductive film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102560362A true CN102560362A (en) | 2012-07-11 |
Family
ID=46406942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100591500A Pending CN102560362A (en) | 2012-03-08 | 2012-03-08 | Method for preparing p-type CuAlO2 transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102560362A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103114269A (en) * | 2013-01-25 | 2013-05-22 | 南京理工大学 | Preparation method of transparent conducting oxide CuAlO2 film |
| CN103173726A (en) * | 2013-03-14 | 2013-06-26 | 杭州电子科技大学 | Preparation method of titanium-doped zinc oxide transparent conducting thin film |
| CN110182839A (en) * | 2019-05-31 | 2019-08-30 | 哈尔滨工业大学 | A method of using copper aluminum oxide film as precursor preparation cupric oxide nano array |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210313A (en) * | 2006-12-29 | 2008-07-02 | 中国科学院长春光学精密机械与物理研究所 | Method for growing MgxZn1-xO film by electron-beam evaporation |
| CN102219494A (en) * | 2011-04-29 | 2011-10-19 | 浙江大学 | Preparation method for P-type CuAlO2 semiconductor material |
-
2012
- 2012-03-08 CN CN2012100591500A patent/CN102560362A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210313A (en) * | 2006-12-29 | 2008-07-02 | 中国科学院长春光学精密机械与物理研究所 | Method for growing MgxZn1-xO film by electron-beam evaporation |
| CN102219494A (en) * | 2011-04-29 | 2011-10-19 | 浙江大学 | Preparation method for P-type CuAlO2 semiconductor material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103114269A (en) * | 2013-01-25 | 2013-05-22 | 南京理工大学 | Preparation method of transparent conducting oxide CuAlO2 film |
| CN103173726A (en) * | 2013-03-14 | 2013-06-26 | 杭州电子科技大学 | Preparation method of titanium-doped zinc oxide transparent conducting thin film |
| CN110182839A (en) * | 2019-05-31 | 2019-08-30 | 哈尔滨工业大学 | A method of using copper aluminum oxide film as precursor preparation cupric oxide nano array |
| CN110182839B (en) * | 2019-05-31 | 2021-07-06 | 哈尔滨工业大学 | Method for preparing copper oxide nano array by using copper-aluminum oxide film as precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20190311889A1 (en) | Synthesis of high-purity bulk copper indium gallium selenide materials | |
| CN103526297B (en) | One prepares topological insulator Bi 2se 3the method of film | |
| CN101958369B (en) | Method for preparing copper-indium-gallium-selenium film material | |
| CN104835869B (en) | Copper-indium-galliun-selenium film solar cell and preparation method thereof | |
| Wang et al. | A review of earth abundant ZnO-based materials for thermoelectric and photovoltaic applications | |
| Bansal et al. | Growth control of molybdenum thin films with simultaneously improved adhesion and conductivity via sputtering for thin film solar cell application | |
| CN102560362A (en) | Method for preparing p-type CuAlO2 transparent conductive film | |
| CN104726825B (en) | A kind of preparation method of p-type electrically conducting transparent cobalt/cobalt oxide metal nanocomposite films | |
| CN102312293B (en) | Method for growing large size Ta2O5 single crystal by using floating zone method | |
| CN103173726A (en) | Preparation method of titanium-doped zinc oxide transparent conducting thin film | |
| CN103060757B (en) | Method for growing p-type transparent and conducting Ni1-xMgxO crystal film by doping Li | |
| Sun et al. | Effects of selenization process on densification and microstructure of Cu (In, Ga) Se2 thin film prepared by doctor blading of CIGS nanoparticles | |
| CN102751387A (en) | Preparation method of Cu (In, ga) Se2thin film for absorption layer of thin film solar cell | |
| KR20110098753A (en) | Method for manufacturing a powder for the production of p-type transparent conductive films | |
| JP5752624B2 (en) | CZTS compound semiconductor manufacturing method | |
| Singh et al. | One step deposition of Cu2ZnSnSe4 thin films using a ceramic quaternary target | |
| CN102312202A (en) | Zinc oxide-based wide bandgap ceramic target and preparation method thereof | |
| CN105514275A (en) | Methylamine lead iodine based solar cell preparation method based on NiO hole transmission layer | |
| Punitha et al. | Structural and surface morphological studies of magnesium tin oxide thin films | |
| CN103715283B (en) | A kind of solar cell and preparation method thereof | |
| CN104630716B (en) | A kind of transparent Ca of p-type3Co4O9The preparation method of conductive film | |
| TW201331123A (en) | Method for producing the powders of copper-zinc-tin-chalcogenide by sol-gel method | |
| CN103103479A (en) | Method for preparing p-type zinc oxide film through sulfur and nitrogen co-doping | |
| KR101483254B1 (en) | The method of fabricating quarternary Se compounds sintered materials for use of sputtering targets | |
| CN101781749A (en) | Preparation method of Cu doped p type ZnO thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120711 |