CN103805960A - Preparation method of chrome oxide thin film - Google Patents
Preparation method of chrome oxide thin film Download PDFInfo
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- CN103805960A CN103805960A CN201210441646.4A CN201210441646A CN103805960A CN 103805960 A CN103805960 A CN 103805960A CN 201210441646 A CN201210441646 A CN 201210441646A CN 103805960 A CN103805960 A CN 103805960A
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Abstract
The invention relates to a preparation method of a chrome oxide thin film. Metal organic chemical vapor deposition is adopted, and the preparation method comprises following steps: one or more than two selected from argon, hydrogen, and nitrogen are mixed with aqueous vapor, and an obtained mixed gas is taken as a reaction gas; chromium precursor steam is delivered into a deposition chamber, and the chromium precursor is subjected to decomposition reaction in the presence of the reaction gas so as to form the chrome oxide thin film on the surface of a substrate; and substrate by-product is exhausted out of a reaction chamber with the reaction gas. Carbon residual of the chrome oxide thin film prepared via the preparation method can be removed completely; the chrome oxide thin film is flat in surfaces, and compact in structure; and film-substrate binding performance is excellent.
Description
Technical field
The present invention relates to a kind of preparation method of chromium oxide film, be specially the metal organic chemical vapor deposition preparation method of chromium oxide film.The chromium oxide film obtaining can be used for the wear-resistance thin film of material surface, also can be for the corrosion-resistant erosion of metal, resistance to high temperature oxidation, anti-hydrogen infiltration function thin-film material.
Background technology
In the last few years, chromic oxide had received great research concern as film material with function.Chromic oxide hardness is high, frictional coefficient is little, has good abrasion resistance, can be used for the blocking layer of microelectronic device and the protective layer of wearing and tearing device.Chromium oxide film at high temperature possesses good anti-oxidant, corrosion resistance nature, can be used for the high-temperature oxidation resistant thin-film material of metallic surface.In addition, chromic oxide also has very low hydrogen rate of permeation, for the anti-hydrogen osmotic membrane of stainless steel surface high temperature.
At present, the preparation method of chromium oxide film mainly contains in-situ oxidation, method of evaporation, magnetron sputtering, plasma spraying and chemical vapour deposition etc.Metal organic chemical vapor deposition utilizes transmission, absorption, the thermal decomposition process of metal organic precursor method, in substrate surface deposited oxide layer, have depositing temperature low, reproducible, easily realize the advantages such as commercialization.According to bibliographical information, the metal organic chemical vapor deposition technology of chromium oxide film extensively adopts argon gas or nitrogen carrier band oxygen or air as reactant gases, obtained respectively the even chromium oxide film of submicron and micron thickness at substrate surfaces such as silicon single crystal, glass, nickel, stainless steels, more excellent [the people such as J.C.Nable of film-substrate cohesion, wear resisting property of film, Surface and Coatings Technology, 186 (2004) 423; The people such as S.Chevalier, Applied Surface Science, 167 (2000) 125].But, a large amount of results of study shows that the chromium oxide film surfaceness of the atmosphere combination acquisition that has deposition technique use is high and membrane structure loose, cause chromium oxide film to improve nearly order of magnitude [people such as J.C.Nable compared with the stainless steel oxidation weightening finish of compact aluminum oxide film, Surface and Coatings Technology, 186 (2004) 423]; In addition, chromium metal-organic decomposition not exclusively also easily causes in chromium oxide film and exists trace carbon residual, affects the use properties [people such as R.SamuelBoorset, Chemistry of Materials, 6 (1994) 1515] of chromium oxide film.The major cause that produces above-mentioned phenomenon is that the atmosphere combination oxygen partial pressure that adopts of prior art is too high, and precursor thermolysis occurs not arriving substrate surface, and causing film deposition process is diffusion process control, causes chromium oxide film surface irregularity, short texture.
Summary of the invention
The metal organic chemical vapor deposition that the present invention is directed to chromium oxide film has carried out technical optimization, and a kind of method of the chromium oxide film of growing is provided.Adopt in argon gas, nitrogen, hydrogen one or more with the mixed gas of aqueous vapor as reactant gases, adopt aqueous vapor to replace air or oxygen, impel film deposition process to change surface process control into, thereby the surface finish of raising film; In addition, aqueous vapor can also promote the gas such as carbonic acid gas, carbon monoxide of metallorganics thermolysis generation in migration and the desorption of substrate surface, thereby improves sedimentation rate and the compact structure of film.
To achieve these goals, the present invention includes following steps:
A kind of preparation method of chromium oxide film, adopt mocvd method, described method comprises the steps: to adopt in argon gas, hydrogen, nitrogen the mixed gas of one or more and aqueous vapor as reactant gases, chromium precursor steam is transported to sediment chamber's (reaction chamber), chromium precursor issues raw decomposition reaction in above-mentioned reactant gases effect and forms chromium oxide film at substrate surface, and the by product that substrate surface forms goes out reaction chamber by reactant gases carrier band.
Described chromium precursor is chromium organometallics, as chromium acetylacetonate, Chromium hexacarbonyl, hexafluoroacetylacetone chromium etc.
The mixed gas of one or more and aqueous vapor in described argon gas, hydrogen, nitrogen, aqueous vapor volume percent in mixed gas is 1 ~ 10%, the flow of mixed gas is 10 ~ 100sccm.
Reaction chamber pressure maintains 100 ~ 3000Pa scope, and underlayer temperature maintains 300 ~ 800 ℃ of scopes.
Described substrate is monocrystalline substrate or steel substrate etc.
Advantage of the present invention:
(1) chromium precursor steam is transported to reaction chamber by the present invention, use in argon gas, nitrogen, hydrogen the mixed gas of one or more and aqueous vapor as reactant gases, 300 ~ 800 ℃ of temperature ranges, chromium precursor forms chromium oxide film in above-mentioned reaction atmosphere generation decomposition reaction at substrate surface, and substrate by product is discharged reaction chamber by reactant gases carrier band.Compared with existing chromium oxide film technology of preparing, it is residual that the chromium oxide film that adopts the inventive method to obtain can be got rid of in film carbon completely, and film surface is smooth, compact structure, film base binding performance excellence.
(2) introducing of aqueous vapor can improve precursor thermal decomposition product from substrate desorption rate, has improved film deposition rate, and film has better planeness and compactness.
(3) the present invention kept original processing unit cost low, manipulate simple advantage, be convenient to realize and promote.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the chromium oxide film surface topography that traditional method obtains;
Fig. 2 is the chromium oxide film surface topography that uses the present invention to obtain;
Fig. 3 is the X ray diffracting spectrum that uses the chromium oxide film of the present invention's acquisition.
Embodiment
Fig. 1 is the surface topography that uses the chromium oxide film of traditional method acquisition.Adopt mocvd method, film preparation process adopts argon gas as carrier gas, flow is 20sccm, oxygen is as reactant gases, chromium acetylacetonate Heating temperature is 180 ℃, and reaction chamber pressure is 1400 ~ 1600Pa, adopts monocrystalline substrate, depositing temperature is 500 ℃, and depositing time is 1 hour.
As seen from Figure 1, the chromium oxide film surface irregularity that uses traditional method to obtain, the chromic oxide crystal grain that is 0.1 ~ 0.2 micron by particle diameter forms, and in addition, this membrane structure is loose, visible significantly pin hole.
Embodiment 1
Adopt mocvd method to prepare chromium oxide film: monocrystalline substrate is adopted to acetone ultrasonic cleaning 10 minutes, and deionized water ultrasonic cleaning 10 minutes, puts into sediment chamber after substrate is dry.The deposition parameter of chromium oxide film is: chromium acetylacetonate Heating temperature is 180 ℃; Hydrogen and gas-vapor mix gas, as reactant gases, are transported to sediment chamber by chromium precursor steam, and aqueous vapor volume percent is 2 ~ 4%, and flow is 20sccm; Sediment chamber's pressure is 1400 ~ 1600Pa; Depositing temperature is 500 ℃, and depositing time is 1 hour.
Fig. 2 is the SEM photo of this chromium oxide film, and compared with the chromium oxide film obtaining with traditional method in Fig. 1, this film surface is very smooth, simultaneously membrane structure densification.
Embodiment 2
Adopt mocvd method to prepare chromium oxide film: will at the bottom of 316L stainless steel lining, adopt acetone ultrasonic cleaning 10 minutes, ethanol ultrasonic cleaning 10 minutes, deionized water ultrasonic cleaning 10 minutes, puts into sediment chamber after substrate is dry.The deposition parameter of chromium oxide film is: Chromium hexacarbonyl Heating temperature is 200 ℃; Argon gas and gas-vapor mix gas, as reactant gases, are transported to sediment chamber by chromium precursor steam, and the volume percent of aqueous vapor is 3 ~ 5%, and flow is 20sccm; Sediment chamber's pressure is 1500 ~ 1800Pa; Depositing temperature is 600 ℃, and depositing time is 2 hours.
Fig. 3 is the X ray diffracting spectrum of this chromium oxide film, and chromium oxide film is for to be oriented to main hexagonal structure chromic oxide with (110).
Embodiment 3
Adopt mocvd method to prepare chromium oxide film: monocrystalline substrate is adopted to acetone ultrasonic cleaning 10 minutes, and deionized water ultrasonic cleaning 10 minutes, puts into sediment chamber after substrate is dry.The deposition parameter of chromium oxide film is: hexafluoroacetylacetone chromium Heating temperature is 140 ℃; Argon gas, hydrogen, nitrogen (pressing 1:1:1 volume ratio mixes) as reactant gases, are transported to sediment chamber by chromium precursor steam with gas-vapor mix gas, and aqueous vapor volume percent is 2 ~ 4%, and flow is 20sccm; Sediment chamber's pressure is 100 ~ 150Pa; Depositing temperature is 300 ℃, and depositing time is 1 hour.
Embodiment 4
Adopt mocvd method to prepare chromium oxide film: will at the bottom of 316L stainless steel lining, adopt acetone ultrasonic cleaning 10 minutes, deionized water ultrasonic cleaning 10 minutes, puts into sediment chamber after substrate is dry.The deposition parameter of chromium oxide film is: hexafluoroacetylacetone chromium Heating temperature is 190 ℃; Hydrogen, nitrogen (pressing 1:1 volume ratio mixes) as reactant gases, are transported to sediment chamber by chromium precursor steam with gas-vapor mix gas, and aqueous vapor volume percent is 6 ~ 8%, and flow is 50sccm; Sediment chamber's pressure is 2800 ~ 3000Pa; Depositing temperature is 500 ℃, and depositing time is 2 hours.
Embodiment 5
Adopt mocvd method to prepare chromium oxide film: monocrystalline substrate is adopted to acetone ultrasonic cleaning 10 minutes, and deionized water ultrasonic cleaning 10 minutes, puts into sediment chamber after substrate is dry.The deposition parameter of chromium oxide film is: chromium acetylacetonate Heating temperature is 190 ℃; Argon gas, hydrogen (pressing 1:2 volume ratio mixes) as reactant gases, are transported to sediment chamber by chromium precursor steam with gas-vapor mix gas, and aqueous vapor volume percent is 5 ~ 7%, and flow is 80sccm; Sediment chamber's pressure is 2000 ~ 2200Pa; Depositing temperature is 800 ℃, and depositing time is 1 hour.
Observe the prepared chromium oxide film of embodiment 1-5 by scanning electronic microscope (SEM), and compared with the chromium oxide film obtaining with traditional method in Fig. 1, the prepared chromium oxide film surface of embodiment 1-5 is obviously very smooth, membrane structure densification simultaneously, film base binding performance excellence is got rid of in film carbon residual completely simultaneously.
By the X ray diffracting spectrum of the prepared chromium oxide film of embodiment 1-5 is analyzed, can see that chromium oxide film of the present invention is with (110) to be oriented to main hexagonal structure chromic oxide.
In the present invention, reactant gases is the mixed gas of one or more and aqueous vapor in argon gas, hydrogen, nitrogen, as the carrier gas in mocvd method.Wherein, when two or more mixing in argon gas, hydrogen and nitrogen, mix and all can in any proportion.
Chromium precursor steam is by carrier gas carrier band, and its flow can be controlled by precursor Heating temperature, pressure, flow rate of carrier gas etc.Precursor Heating temperature can, preferably between 140 ~ 200 ℃, be distinguished depending on DIFFERENT Cr precursor to some extent.
In the inventive method, the introducing of aqueous vapor has improved precursor thermal decomposition product from substrate desorption rate, has improved film deposition rate, and film has better planeness and compactness.
Claims (7)
1. the preparation method of a chromium oxide film, adopt mocvd method, comprise the steps: to adopt in argon gas, hydrogen and nitrogen the mixed gas of one or more and aqueous vapor as reactant gases, chromium precursor steam is transported to sediment chamber, chromium precursor issues raw decomposition reaction in described reactant gases effect and forms chromium oxide film at substrate surface, and the by product that substrate surface forms goes out reaction chamber by reactant gases carrier band.
2. the preparation method of chromium oxide film as claimed in claim 1, is characterized in that: described chromium precursor is chromium organometallics.
3. the preparation method of chromium oxide film as claimed in claim 2, is characterized in that: described chromium organometallics is chromium acetylacetonate, Chromium hexacarbonyl or hexafluoroacetylacetone chromium.
4. the preparation method of chromium oxide film as claimed in claim 1, is characterized in that: the volume percent of described aqueous vapor in mixed gas is 1 ~ 10%.
5. the preparation method of chromium oxide film as claimed in claim 4, is characterized in that: the flow of described mixed gas is 10 ~ 100sccm.
6. the preparation method of chromium oxide film as claimed in claim 1, is characterized in that: the pressure of described sediment chamber is 100 ~ 3000Pa, underlayer temperature is 300 ~ 800 ℃.
7. the preparation method of chromium oxide film as claimed in claim 6, is characterized in that: described substrate is monocrystalline substrate or steel substrate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101082124A (en) * | 2007-05-08 | 2007-12-05 | 中国科学院上海光学精密机械研究所 | Method for developing m-face or a-face ZnO film by metal organic chemical vapour deposition |
| CN101094935A (en) * | 2004-12-28 | 2007-12-26 | 昭和砚壳石油株式会社 | Mothod for producing zno-based transparent electroconductive film by MOCVD(metal organic chemical vapor deposition) method |
| CN101696492A (en) * | 2009-10-23 | 2010-04-21 | 北京航空航天大学 | Device and method for preparing aluminum-doped zinc oxide transparent conductive film |
| CN201942747U (en) * | 2010-12-24 | 2011-08-24 | 河北汉盛光电科技有限公司 | Sprinkler of organic chemical vapor deposition reactor of metal |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101094935A (en) * | 2004-12-28 | 2007-12-26 | 昭和砚壳石油株式会社 | Mothod for producing zno-based transparent electroconductive film by MOCVD(metal organic chemical vapor deposition) method |
| CN101082124A (en) * | 2007-05-08 | 2007-12-05 | 中国科学院上海光学精密机械研究所 | Method for developing m-face or a-face ZnO film by metal organic chemical vapour deposition |
| CN101696492A (en) * | 2009-10-23 | 2010-04-21 | 北京航空航天大学 | Device and method for preparing aluminum-doped zinc oxide transparent conductive film |
| CN201942747U (en) * | 2010-12-24 | 2011-08-24 | 河北汉盛光电科技有限公司 | Sprinkler of organic chemical vapor deposition reactor of metal |
Non-Patent Citations (2)
| Title |
|---|
| G.CARTA.ET.AL: ""Chromium oxide wear and corrosion protection coatings deposited via MOCVD"", 《THERMOCHIMICA ACTA》 * |
| GIOVANNI CARTA.ET.AL: ""A Comparatice Study of Cr2O3 Thin Films Obtained by MOCVD using Three Different Precursors"", 《CHEMICAL VAPOR DEPOSITION》 * |
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Application publication date: 20140521 |