CN106756831A - A kind of preparation method of cupric oxide semiconductive thin film - Google Patents
A kind of preparation method of cupric oxide semiconductive thin film Download PDFInfo
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- CN106756831A CN106756831A CN201611226700.8A CN201611226700A CN106756831A CN 106756831 A CN106756831 A CN 106756831A CN 201611226700 A CN201611226700 A CN 201611226700A CN 106756831 A CN106756831 A CN 106756831A
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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
- C23C14/34—Sputtering
- C23C14/3485—Sputtering using pulsed power to the target
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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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
- C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/087—Oxides of copper or solid solutions thereof
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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
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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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
- C23C14/34—Sputtering
- C23C14/3457—Sputtering using other particles than noble gas ions
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Abstract
The invention discloses a kind of preparation method of cupric oxide semiconductive thin film, the preparation method universality is good, equipment requirement is low, it is simple to prepare, reproducible, using pulsed laser deposition, by the doping of metallic tin, p-type CuO film is formed on substrate, the p-type CuO film resistivity for obtaining is low, carrier concentration is high.
Description
Technical field
The present invention relates to semiconductor film material preparing technical field, and in particular to a kind of system of cupric oxide semiconductive thin film
Preparation Method.
Background technology
Transparent conductive oxide film was always the focus of photoelectric field in recent years, wherein ito thin film be at present research and
Most widely used transparent conductive oxide (TCO) film, various photoelectricity are widely used in because of its good photoelectric characteristic
Device, but because the prices of raw materials are expensive, indium resource is rare and environment is polluted, so as to limit its development and application.
Cupric oxide is a kind of important semi-conducting material, and its optical energy gap is 1.2eV-1.9eV.With sunshine power spectrum
Close, thus have preferable absorbability to sunshine, its theoretical conversion efficiency is 31%, thus be it is a kind of it is ideal too
Positive energy battery material.And in most cases natural cupric oxide is shown as p-type conductivity, this is due to intrinsic defect copper
The presence in room.Possess substantial amounts of copper resource on earth, thus cupric oxide has the relatively low spy of cheap, preparation cost
Point, becomes a kind of material with extensive use.Solar cell, photochemical catalyst, electrode material, resistance-variable storing device,
The aspects such as superconductor, hydrogen manufacturing, photochromic have very strong application.But because the resistivity of CuO film material is higher, load
Flow sub- concentration relatively low, thus have impact on the performance of cupric oxide electronics and opto-electronic device.Therefore, the electric property for preparing is sought
P-type CuO film method it is extremely important.
The content of the invention
The present invention provides a kind of preparation method of cupric oxide semiconductive thin film, and the preparation method universality is good, equipment requirement
It is low, prepare it is simple, reproducible, using pulsed laser deposition, by the doping of metallic tin, on substrate formed p-type oxidation
Copper thin film, the p-type CuO film resistivity that obtains is low, carrier concentration is high.
To achieve these goals, the invention provides a kind of preparation method of cupric oxide semiconductive thin film, the method bag
Include following steps：
（1）Prepare target
Cupric oxide powder is mixed with glass putty, the mass content of the glass putty of doping is 1%, and then material powder is carried out at ball milling
Reason, obtains fine size and uniform spherical particle；
Treated powder is carried out die-filling；
Isostatic cool pressing is carried out after die-filling, pressure limit 100MPa-200MPa is then fired, and baking temperature range is 1200
℃-1500℃；
Semi-finished product are obtained after firing, semi-finished product is machined after standing cooling, it is ensured that interior positive camber is smooth, obtains
Target.
（2）Treatment substrate
Grinding and polishing simultaneously cleans glass substrate, standby；
（3）During above-mentioned target is placed in the settling chamber of pulse laser deposition equipment with above-mentioned substrate, settling chamber is evacuated to 1
×10-3Below Pa, heating substrate opens oxygen ventilation valve to 480-500 DEG C, and oxygen is passed through to settling chamber, regulation settling chamber
Pressure is 8-12Pa, then bombards target, the deposited oxide Copper thin film on substrate, pulse laser with KrF excimer pulsed lasers
Frequency be 5-10Hz, sedimentation time be 1-2 hour, deposit terminate after, naturally cool to room temperature, obtain p-type CuO film.
Preferably, in the step（2）In, the grinding and polishing can be first on the boart boart wheel disc of 600 mesh by substrate
Corase grind 10min is carried out, fine grinding 10min is then carried out on the boart boart wheel disc of 1200 mesh, then with the diamond polishing of W2.5
Powder is polished, the ultrasonic cleaning uniformly bright to specimen surface, can in the following order clean the substrate after grinding and polishing,
Acetone is cleaned by ultrasonic 5min → absolute ethyl alcohol stand-by, the ion gun cleaning that is cleaned by ultrasonic 5min → drying, can use Hall from
Component carries out cleaning 5min to substrate, and pressure is 2 × 10-2Pa, underlayer temperature is 300 DEG C, and argon gas flux is 10sccm, bias
It is -100V, cathode current is 29.5A, and cathode voltage is 19V, and anode current is 7A, and anode voltage is 80V, to remove substrate table
The adsorbed gas in face and impurity, improve the bond strength and quality of forming film of sputtering layer and substrate.
Specific embodiment
Embodiment one
Cupric oxide powder is mixed with glass putty, the mass content of the glass putty of doping is 1%, and then material powder is carried out at ball milling
Reason, obtains fine size and uniform spherical particle；Treated powder is carried out die-filling；Isostatic cool pressing is carried out after die-filling,
Pressure limit 100MPa, is then fired, and baking temperature range is 1200 DEG C DEG C；Semi-finished product are obtained after firing, cooling is stood
Semi-finished product are machined afterwards, it is ensured that interior positive camber is smooth, obtains target.
Grinding and polishing simultaneously cleans glass substrate, standby.The grinding and polishing, can be by substrate first in the boart boart of 600 mesh
Corase grind 10min is carried out on wheel disc, fine grinding 10min is then carried out on the boart boart wheel disc of 1200 mesh, then with the Buddha's warrior attendant of W2.5
Stone polishing powder is polished, the ultrasonic cleaning uniformly bright to specimen surface, can be by the substrate after grinding and polishing by following suitable
Sequence is cleaned, and acetone ultrasonic cleaning 5min → absolute ethyl alcohol ultrasonic cleaning 5min → drying is stand-by, and the ion gun cleaning can be used
Hall ion source carries out cleaning 5min to substrate, and pressure is 2 × 10-2Pa, underlayer temperature is 300 DEG C, and argon gas flux is 10sccm,
It is -100V to bias, and cathode current is 29.5A, and cathode voltage is 19V, and anode current is 7A, and anode voltage is 80V, to remove lining
The adsorbed gas of basal surface and impurity, improve the bond strength and quality of forming film of sputtering layer and substrate.
During above-mentioned target is placed in the settling chamber of pulse laser deposition equipment with above-mentioned substrate, settling chamber is evacuated to
1×10-3Below Pa, heating substrate opens oxygen ventilation valve to 480 DEG C, and oxygen is passed through to settling chamber, adjusts the pressure of settling chamber
It is 8Pa, then bombards target, the deposited oxide Copper thin film on substrate with KrF excimer pulsed lasers, the frequency of pulse laser is
5Hz, sedimentation time is 1 hour, after deposition terminates, naturally cools to room temperature, obtains p-type CuO film.
Embodiment two
Cupric oxide powder is mixed with glass putty, the mass content of the glass putty of doping is 1%, and then material powder is carried out at ball milling
Reason, obtains fine size and uniform spherical particle；Treated powder is carried out die-filling；Isostatic cool pressing is carried out after die-filling,
Pressure limit 200MPa, is then fired, and baking temperature range is 1500 DEG C；Semi-finished product are obtained after firing, after standing cooling
Semi-finished product are machined, it is ensured that interior positive camber is smooth, obtains target.
Grinding and polishing simultaneously cleans glass substrate, standby.The grinding and polishing, can be by substrate first in the boart boart of 600 mesh
Corase grind 10min is carried out on wheel disc, fine grinding 10min is then carried out on the boart boart wheel disc of 1200 mesh, then with the Buddha's warrior attendant of W2.5
Stone polishing powder is polished, the ultrasonic cleaning uniformly bright to specimen surface, can be by the substrate after grinding and polishing by following suitable
Sequence is cleaned, and acetone ultrasonic cleaning 5min → absolute ethyl alcohol ultrasonic cleaning 5min → drying is stand-by, and the ion gun cleaning can be used
Hall ion source carries out cleaning 5min to substrate, and pressure is 2 × 10-2Pa, underlayer temperature is 300 DEG C, and argon gas flux is 10sccm,
It is -100V to bias, and cathode current is 29.5A, and cathode voltage is 19V, and anode current is 7A, and anode voltage is 80V, to remove lining
The adsorbed gas of basal surface and impurity, improve the bond strength and quality of forming film of sputtering layer and substrate.
During above-mentioned target is placed in the settling chamber of pulse laser deposition equipment with above-mentioned substrate, settling chamber is evacuated to
1×10-3Below Pa, heating substrate opens oxygen ventilation valve to 500 DEG C, and oxygen is passed through to settling chamber, adjusts the pressure of settling chamber
It is 12Pa, then bombards target, the deposited oxide Copper thin film on substrate, the frequency of pulse laser with KrF excimer pulsed lasers
It is 10Hz, sedimentation time is 2 hours, after deposition terminates, naturally cools to room temperature, obtains p-type CuO film.
Claims (2)
1. a kind of preparation method of cupric oxide semiconductive thin film, the method comprises the following steps：
（1）Prepare target
Cupric oxide powder is mixed with glass putty, the mass content of the glass putty of doping is 1%, and then material powder is carried out at ball milling
Reason, obtains fine size and uniform spherical particle；
Treated powder is carried out die-filling；
Isostatic cool pressing is carried out after die-filling, pressure limit 100MPa-200MPa is then fired, and baking temperature range is 1200
℃-1500℃；
Semi-finished product are obtained after firing, semi-finished product is machined after standing cooling, it is ensured that interior positive camber is smooth, obtains
Target.
（2）Treatment substrate
Grinding and polishing simultaneously cleans glass substrate, standby；
（3）During above-mentioned target is placed in the settling chamber of pulse laser deposition equipment with above-mentioned substrate, settling chamber is evacuated to 1
×10-3Below Pa, heating substrate opens oxygen ventilation valve to 480-500 DEG C, and oxygen is passed through to settling chamber, regulation settling chamber
Pressure is 8-12Pa, then bombards target, the deposited oxide Copper thin film on substrate, pulse laser with KrF excimer pulsed lasers
Frequency be 5-10Hz, sedimentation time be 1-2 hour, deposit terminate after, naturally cool to room temperature, obtain p-type CuO film.
2. the method for claim 1, it is characterised in that in the step（2）In, the grinding and polishing can be by substrate
Corase grind 10min first is carried out on the boart boart wheel disc of 600 mesh, then fine grinding is carried out on the boart boart wheel disc of 1200 mesh
10min, then, the ultrasonic cleaning uniformly bright to specimen surface is polished with the diamond polishing powder of W2.5, will can grind
Substrate after polishing is cleaned in the following order, and acetone ultrasonic cleaning 5min → absolute ethyl alcohol ultrasonic cleaning 5min → drying is stand-by,
The ion gun cleaning, can carry out cleaning 5min to substrate using hall ion source, and pressure is 2 × 10-2Pa, underlayer temperature is
300 DEG C, argon gas flux is 10sccm, and it is -100V to bias, and cathode current is 29.5A, and cathode voltage is 19V, and anode current is
7A, anode voltage is 80V, to remove adsorbed gas and the impurity of substrate surface, improves the bond strength of sputtering layer and substrate
And quality of forming film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611226700.8A CN106756831A (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method of cupric oxide semiconductive thin film |
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| CN201611226700.8A CN106756831A (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method of cupric oxide semiconductive thin film |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nano-structured nitrogen silicon zirconium coating on surface of hard alloy substrate |
| CN105063559A (en) * | 2015-08-17 | 2015-11-18 | 基迈克材料科技（苏州）有限公司 | Zr element-doped AZO target material with enhanced photoelectric property |
| CN105779939A (en) * | 2016-03-24 | 2016-07-20 | 陕西师范大学 | Preparation method of p type copper oxide thin film with low resistivity and high carrier concentration |
-
2016
- 2016-12-27 CN CN201611226700.8A patent/CN106756831A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921982A (en) * | 2010-09-06 | 2010-12-22 | 厦门大学 | Method for preparing nano-structured nitrogen silicon zirconium coating on surface of hard alloy substrate |
| CN105063559A (en) * | 2015-08-17 | 2015-11-18 | 基迈克材料科技（苏州）有限公司 | Zr element-doped AZO target material with enhanced photoelectric property |
| CN105779939A (en) * | 2016-03-24 | 2016-07-20 | 陕西师范大学 | Preparation method of p type copper oxide thin film with low resistivity and high carrier concentration |
Non-Patent Citations (1)
| Title |
|---|
| JING WU,ET AL.: "Characterization of Sn-doped CuO thin films prepared by a sol-gel method", 《J MATER SCI: MATER ELECTRON》 * |
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