CN1242094C - Method for preparing film by liquid phase source atomizing and microwave plasma chemical gaseous deposition - Google Patents
Method for preparing film by liquid phase source atomizing and microwave plasma chemical gaseous deposition Download PDFInfo
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- CN1242094C CN1242094C CN 03121933 CN03121933A CN1242094C CN 1242094 C CN1242094 C CN 1242094C CN 03121933 CN03121933 CN 03121933 CN 03121933 A CN03121933 A CN 03121933A CN 1242094 C CN1242094 C CN 1242094C
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Abstract
The present invention relates to a method for preparing films by liquid phase source atomizing and microwave plasma chemical gaseous deposition. The present invention is completed by the following steps: 1, preparing a liquid phase atomized source; 2, exciting chemical reaction by plasma bodies; 3, forming films. The present invention has the advantages: 1, mixed liquid phase is atomized to be used as a reaction source to enlarge material selecting range for preparing film by the traditional gas phase method, and especially soluble inorganic salts are used as raw materials in conformity with resource superiority of China; 2, plasma bodies are excited to generate chemical reaction by microwave energy, are not generated by ordinary high voltage and high frequency to cause chemical reaction to be carried out in the environment of high energy state, large density, no pollution and high vacuum, and are suitable for various chemical reaction types; 3, the present invention can realize film structure control such as formed porous films, or dense films by technology control for regulating parameters such as vacuum degree, deposition rate, substrate temperature, etc., to satisfy various performance requirements.
Description
Technical field
The invention belongs to the Materials science engineering, particularly a kind of liquid phase source atomizing microwave plasma CVD prepares the method for film.
Background technology
Thin-film material is just more and more widely used in modern science and technology and life, as at ferroelectric, dielectric, photoelectron, sensitivity, superconduction, anticorrosion, wear-resisting and decoration etc. a lot of development and application spaces being arranged.Advantages such as film preparing technology correspondingly also develops rapidly, and chemical legal system film is simple and easy to do with it, and process is controlled become the main flow of masking technique gradually.
Sol-gel method in the chemical method (Sol-Gel) demonstrates the advantage of preparation complex component film, but because film process needs repeatedly biofilm and thermal treatment repeatedly, the cycle is longer, influences its stable performance and efficient.
General chemistry vapour deposition (CVD) method is reacted the restriction of gaseous sources, the face of drawing materials is narrow, though the appearance of metallorganics vaporizer chemical vapour deposition (LSCVD) masking technique is taken on a new look this shortcoming to some extent, but carrying out along with reaction, the vaporization rate of reaction source and concentration decay make technological process restive.Costing an arm and a leg and the kind shortage of metallorganics also is a major issue that limits its development in addition.
Solution atomization deposition (LMD) directly deposits to soluble salt solution on the substrate through atomizing, be fit to the preparation multi-component material, but film-forming process does not have links such as after chemical reaction and solid-state phase changes, must carry out sintering thermal treatment to substrate after deposition and could form the solid state crystallization film, its porousness and ununiformity are inevitable.The Japan scholar prepares at solution atomization and also introduces the microwave plasma technology in the superconducting thin film process, but it uses solution atomization, multi-component material is not carried out whole solation design, also do not relate to the control of chemical reaction and thin film growth process, its application is restricted.
Summary of the invention
The purpose of this invention is to provide the method that a kind of liquid phase source atomizing microwave plasma CVD prepares film.It is to use the initial reaction raw material of liquid phase source as chemical vapour deposition, also directly makes the solid product particle be deposited on the novel process that forms thin-film material on the substrate with microwave plasma excitated chemical reaction.This technology has that the system film is simple, convenient and rapid, film-forming temperature is low, coverage is high, and component uniformity is good, be fit to characteristics such as preparation complex component, not only can prepare dense film, also can prepare porous-film, and is widely applicable.
Technology of the present invention is achieved in that
This liquid phase source atomizing microwave plasma CVD prepares the method for film, and concrete steps are as follows:
(1) preparation in liquid phase atomizing source
Select soluble salt to be system pleurodiaphragmatic in terspace material, with thin-film material by the stoichiometric ratio of its composition carry out raw material calculating and accurately weigh after, be dissolved in the different solvents respectively according to the deliquescent difference of its salt, the homogeneous solution of each self-forming 0.3mol/L-1.0mol/L, then that above solution is neutral by the acid back of elder generation, last alkaline order adds mixing respectively; Be modulated into the aerosolizable even colloidal sol or the solution of 0.06mol/L-0.2mol/L concentration at last, as liquid phase atomizing source;
(2) plasma exciatiaon chemical reaction process
Above liquid phase colloidal sol or solution are carried out ultrasonic atomizatio, with atomization gas with in the 10-30ml/min flow feeding reaction chamber, under the microwave generator effect, the high enthalpy microwave plasma of the high temperature that in reaction chamber, has inspired, with the little droplet that imports, meet the thin-film material stoichiometric ratio, at first gasification, and then take place to decompose and ionization, ion formed.These are through ionized ion, electronics, and neutral molecule, and activity is very high each other, chemical reaction takes place, when breaking away from the high-temperature plasma tagma under the effect of air-flow, owing to high thermograde occurs, cold soon rapidly, make gaseous product form the solid product particle rapidly, be deposited on the substrate.
(3) forming process of film
Solid phase particles through above chemical gas phase reaction generates under the drive of air-flow, will clash into substrate base, and part is under deposition on the substrate.Substrate temperature can be controlled by well heater, usually in the sedimentary initial stage, substrate temperature is controlled at 500-650 ℃, and this low relatively temperature helps depositing the nucleation of solid phase particles on substrate of getting off.Along with the carrying out of deposition process, in the sedimentary middle and later periods, usually temperature is controlled between 650-850 ℃, this high relatively depositing temperature helps growth for Thin Film, reaches the crystallinity film that use properties requires.
Be described in detail concrete grammar of the present invention below again:
1. the preparation in liquid phase atomizing source
It is system pleurodiaphragmatic in terspace material that the present invention mainly selects soluble inorganic salt, can be suitable for especially existing already used organic salt certainly, and the initial reaction raw material of chemical gas phase reaction is provided with the liquid phase atomizing.The raw material of liquid phase is like this preparation: after earlier thin-film material being carried out the calculating of raw material by the stoichiometric ratio of its composition and accurately weighing, in its deliquescent different organic solvents of water-soluble solvent or ethanol etc. respectively, the homogeneous solution of each self-forming 0.3mol/L-1.0mol/L, then that above solution is neutral by the acid back of elder generation, the order of last alkalescence adds mixing respectively, forms homogeneous mixture solotion.To polycomponent solution, need to introduce complexing agent or the cross-linking agent solution that easily forms complex structure as citric acid, ethylene glycol etc., solution to slant acidity needs to introduce to make the abundant complexing of each component of above mixing solutions and be transformed into stable sols as ethylenediamine tetraacetic acid (EDTA) complexing agents such as (EDTA) again, to increase the liquid phase homogeneity.Be modulated into the aerosolizable even colloidal sol of 0.06mol/L-0.2mol/L concentration at last, can directly utilize its solution, form liquid phase atomizing source like this single component material.
2. plasma exciatiaon chemical reaction process
Above liquid phase colloidal sol or solution 2 are inserted in the glass volumetric flask that is complementary with spraying gun, be placed in the accompanying drawing one on the ultrasonic atomizer 1, spraying gun power is 50-100W, carries out ultrasonic atomizatio.Usually with the argon gas of easily ionizable or direct be under the drive of supporting gas 3 with the reaction gas, atomization gas is imported in the reaction chamber 7 through mass flowmeter 4 with the 10-30ml/min flow, as the reacting gas concentration deficiency, can in another road 5, import through mass flowmeter 4 with the 10-50ml/min flow.At this moment, under microwave generator 6 effects of the 500-800W of 2.45GHz power, the high enthalpy microwave plasma of high temperature that has inspired at reaction chamber 8 places, with what import, the little droplet that meets the thin-film material stoichiometric ratio, at first gasification, and then take place to decompose and ionization, forming ion, these are through ionized ion, electronics, and neutral molecule, activity is very high each other, and chemical reaction takes place, when breaking away from the high-temperature plasma tagma under the effect of air-flow, owing to high thermograde occurs, cold soon rapidly, make gaseous product form the solid product particle rapidly, be deposited on substrate 10 places.
3. the forming process of film
Solid phase particles through above chemical gas phase reaction generates under the drive of air-flow, will clash into substrate base, and part is under deposition on the substrate.Substrate temperature can be controlled by the well heater on the pallet 12 11.Usually in the sedimentary initial stage, substrate temperature is controlled at 500-650 ℃, this low relatively temperature helps depositing the nucleation of solid phase particles on substrate of getting off.Along with the carrying out of deposition process, in the sedimentary middle and later periods, usually temperature is controlled between 650-850 ℃, this high relatively depositing temperature helps growth for Thin Film.Processes such as the diffusion that the reaction product particle takes place on substrate, migration, arrangement forming continuous, fine and close film and to reach design of thin mould material composition mutually, thereby directly are designed to reach the crystallinity film that use properties requires.
In deposition process, by the micromotor under the substrate pallet substrate is rotated with 2 rev/mins speed, make the thin-film material homogenizing that is deposited on the substrate.In deposition process, the pressure in the quartz glass reaction chamber 9 maintains between the 100-600Pa by vacuum pump 13.Above film-forming process processing parameter can be realized automatization control and monitoring by computer 14.Regulate by time control and sedimentation rate, can be deposited as certain thickness film.Time, between 20-100 minute, thickness was at 100-1000nm usually.Can directly control formation crystallinity film to general thin-film material,, can after deposition reaction finishes, put into further anneal of heat treatment furnace together with substrate, so that the material crystallization is complete to the thin-film material of material composition and phase structure complexity.
Film-forming method of the present invention, combine the advantage of traditional liquid phase legal system film and gas phase legal system film, not only be suitable for one-component system, be particularly suited for the preparation of multi-component complex system thin-film material, broken through the limitation of existing film-forming method, all significant to film preparing technology and thin-film material development.We successfully adopting said method prepared multiple film, reach effect preferably.
The present invention one adopts the solubility salt, and particularly adopting soluble inorganic salt is characteristic of the present invention.Comprise nitrate in these salt: as Sr (NO)
2, Ba (NO)
2, Pb (NO)
2, Mn (NO)
2, Bi (NO)
3, Y (NO)
3, La (NO)
3Deng; Chloride salt: as SrCl
2, CuCl
2, CaCl
2, FeCl
3, SnCl
4Deng; Vitriol; As ZnSO
4, NiSO
4, CuSO
4Deng; Citrate trianion: as Tiorco 677, citric acid zirconium etc.; Other class salt such as Platinic chloride, ammonium molybdate, permanganate etc.Acetate in the organic salt is as lead acetate, acetate niobium, acetate titanium etc. and all be included among this patent as metal alcohols such as ethanol niobium, ethanol lead, titanium ethanolate, metal lipid, metal ketone etc.Above blended liquid phase atomizing as reaction source, has been enlarged the selection range of conventional gas-phase legal system film, and especially adopting soluble inorganic salt is raw material, meets the china natural resources advantage; The 2nd, by micro-wave energy activated plasma generation chemical reaction, but not produce plasma body with common high pressure, high frequency, chemical reaction is carried out in energy state height, big, the free of contamination high vacuum environment of density, be fit to the number of chemical reaction type; The 3rd, by technology controlling and process,, can realize membrane structure control as parameter regulation such as vacuum tightness, sedimentation rate, underlayer temperatures, as forming porous-film or dense film, satisfy all kinds of performance requriementss.
This method not only is applicable to experimental system film, also can be used for producing.Suitably improve by technological process in addition, also can be used for preparing the technical fields such as surface modification of nano-powder, nanotube, material.
Description of drawings
Fig. 1: microwave plasma CVD film forming apparatus organigram;
The scanning electronic microscope shape appearance figure of preparation film among Fig. 2: the embodiment 1;
The scanning electronic microscope shape appearance figure of preparation film among Fig. 3: the embodiment 2;
The scanning electronic microscope shape appearance figure of preparation film among Fig. 4: the embodiment 3.
Embodiment
Embodiment 1:SrTiO
3The preparation of ceramic membrane.
1.SrTiO
3The preparation in film presoma atomizing source
Adopt TiCl
4And Sr (NO
3)
2Soluble inorganic salt is an initial feed.At first, get the 150ml dehydrated alcohol in dissolve measuring bottle, in stink cupboard with TiCl
4The about 15ml of solution pours in the ethanolic soln and mixes, because TiCl
4In the volatilization of air camber, after the two forms even mixed solution, need to carry out concentration calibration through plasma emission spectroscopy (ICP) method.This time be preparation SrTiO
3Film and the TiCl for preparing
4The concentration of ethanolic soln is 0.46mol/L.Accurate again weighing Sr (NO
3)
2Raw material 21.2 gram, to be adjusted to pH value be in 2 the sour water with its nitric acid that passes through that is dissolved in 200ml, formation 0.5mol/l concentration solution.
With the above-mentioned Sr (NO for preparing
3)
2Acidic aqueous solution is got 20ml and is placed dissolve measuring bottle, adds TiCl in stirring gradually
4Ethanolic soln 21.8ml makes uniform Sr: Ti=1: 1 ethanol and water mixed solution.The aqueous citric acid solution 6.3ml that add 0.8mol/L this moment again is a complexing agent, adds the water of 51.9ml again, and more than 2 hours, forming concentration at last is the aerosolizable colloidal sol of 0.1mol/L 40 ℃ of following homogenizing.
2. microwave plasma excitated gas-phase chemical reaction.
Above mixing solutions is atomized through the ultrasonic device of 75W, at carrier gas O
2Drive under import in the quartz tube reactor with the flow of 20ml/min, reactor has been subjected to the effect that microwave generator power is the microwave plasma of 700W before this, like this atomization gas of Yin Ruing and carrier gas O
2Under the effect of high temperature high energy, gasify, decomposition, ionization, gas-phase chemical reaction takes place subsequently, it is 600 ℃ Al that reaction product deposits to temperature
2O
3On the substrate.
3. the formation of film.
Solid phase particles through above chemical gas phase reaction generates has SrTiO
3Particle also has SrO and TiO
2Particle can be under deposition on the substrate.At sedimentary preceding 20 minutes, with 600 ℃ of substrate temperature controls, temperature is controlled at 700 ℃ back 30 minutes of deposition, to finish the nucleation and growth process of film, form continuous, fine and close SrTiO at last
3Film.
In deposition process, substrate rotates with 2 rev/mins speed, and vacuum tightness maintains 300-450Pa, and the time is 50 minutes, the about 600nm of the thickness of formation.
The SrTiO of 700 ℃ of underlayer temperature deposit preparations
3The stereoscan photograph of film sees that therefrom film particle particle spherical in shape and yardstick are evenly distributed densification as shown in Figure 2.See that from the X diffraction phase composite analysis of film highest peak and time strong peak all are SrTiO
3The phase collection of illustrative plates, Al
2O
3The substrate peak has been withdrawn to less important, and does not find SrO or TiO
2Other phase, prove to have formed the intact single phase SrTiO of crystal form under this temperature
3Film.
To this SrTiO
3Film has also carried out the oxygen sensitivity test, and along with the raising of oxygen partial pressure, the film sample resistance decreasing is at O in probe temperature and test oxygen partial pressure scope in discovery
2+ N
2Under the atmosphere, oxygen concn changes at 20% o'clock by 1%, its resistance value changes to 2.5M Ω by 5.0M Ω, has shown preferably the sensitive features to oxygen.
Embodiment 2:SrBi
2Ta
2O
9The preparation of ceramic membrane.
1.SrBi
2Ta
2O
9The preparation in film presoma atomizing source
(1) takes by weighing Bi (NO
3)
35H
2O raw material 29.1 gram adds 36% the salpeter solution of 20ml, is heated to 50 ℃, stirs 30 minutes to the solution clarification, adds water 100ml and is diluted to 0.5mol/l concentration, and is stand-by after the cooling.(2) accurately take by weighing Ta powder 6 gram, add in the 5ml hydrofluoric acid and at room temperature dissolved 2 days, treat that it all after the dissolving, adds water 55ml and be diluted to 0.55mol/l concentration.(3) preparation Sr salts solution: accurate weighing Sr (NO
3)
2Raw material 21.2 grams are dissolved in it in 200ml water, form 0.5mol/l concentration solution.
SrBi
2Ta
2O
9Being formulated as follows of film presoma atomizing source: at first the about 10ml of the aqueous citric acid solution of 0.25mol/l concentration is contained in a 150ml beaker, add the Bi (NO of the 0.5mol/l for preparing then
3)
3Solution 20ml stirs and forms uniform citric acid-based Bi solution.Splash into the Sr (NO of 0.5mol/l
3)
2Solution 8ml, the same stirring forms uniform citric acid-based Bi+Sr mixing solutions.Splash into 0.55mol/l fluorotantalic acid solution 14.5ml more gradually, stir more than 30 minutes, form the mixed solution of Bi+Sr+Ta, wherein Bi is excessive about 25%, the ferroelectric properties that is used to compensate volatilization loss He improves material.To splash into the ethylene glycol solution 6ml that concentration is 0.25mol/l in the above mixing solutions, and be heated to 50 ℃, form polyreaction, stirred 3 hours.Add the ethylenediamine tetraacetic acid (EDTA) that 6ml concentration is 0.25mol/l (EDTA) ammonia soln behind the cool to room temperature again, be used to regulate acid-basicity and polyreaction is further carried out, stirred 3 hours, and place more than 3 days, form the stable SrBi that contains at last
2Ta
2O
9Concentration is the Bi+Sr+Ta mixed sols of 0.062mol/l.
2. microwave plasma excitated gas-phase chemical reaction.
This step is with example 1, and different is, and reactor is subjected to microwave generator power is 800W, and it is 650 ℃ Pt/Ti/SiO that reaction product deposits to temperature
2On/Si the substrate.
3. the formation of film.
This step is with example 1, and different is that the solid phase particles of generation has SrBi
2Ta
2O
9Particle also has SrO, Ta
2O
5And Bi
2O
3Particle, they will be under deposition on the substrate.At sedimentary preceding 20 minutes,, temperature is controlled at 700 ℃ back 40 minutes of deposition with 650 ℃ of substrate temperature controls.Vacuum tightness maintains 400-600Pa, and the time is 60 minutes, the about 450nm of the thickness of formation.The film that form this moment is also failed complete crystallization, needs after deposition again through 750 ℃, and anneal under 40 minutes oxidizing atmospheres forms crystalline film at last.
SrBi from preparation
2Ta
2O
9See among the stereoscan photograph of film such as Fig. 3 that the film particle is ellipsoid or long column shape particle and yardstick and is evenly distributed densification.See that from the X diffraction phase composite analysis of film main peaks is SrBi
2Ta
2O
9The phase collection of illustrative plates also has few part Bi
2O
3The peak, and do not find SrO or Ta
2O
5Other phase.
To this SrBi
2Ta
2O
9Film has carried out the ferroelectric properties test, and the electrical property result who is adding ± recording under the 3.5V voltage is that ferroelectric residual polarization value is 2P
r=3.8 μ C/cm
2, coercive electric field is 2E
c=62kV/cm.Shown certain ferroelectric properties.
Embodiment 3:TiO
2The preparation of ceramic membrane.
1.TiO
2The preparation in film presoma atomizing source.
This step is with the TiCl in the example 1
4The preparation of ethanolic soln becomes the aerosolizable solution of 0.1mol/L to get final product with alcohol dilution.
2. microwave plasma excitated gas-phase chemical reaction.
This step is with example 1.
3. the formation of film.
This step is with example 1, and different is, and that to produce may be TiO
2Particle.At sedimentary preceding 20 minutes,, temperature is controlled at 650 ℃ back 20 minutes of deposition with 600 ℃ of substrate temperature controls.Vacuum tightness maintains 300-400Pa, and the time is 40 minutes.From its stereoscan photograph as shown in Figure 4, form continuous, porous TiO at last
2Film, the about 400nm of thickness.
The present invention open and the method and the technology of preparing that propose, those skilled in the art can be by using for reference this paper content, and links such as appropriate change raw material, processing parameter, structure design realize.Method of the present invention and technology are described by preferred embodiment, person skilled obviously can be in not breaking away from content of the present invention, spirit and scope to method as herein described with technology is changed or suitably change and combination, be embodied as membrane technique.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (9)
1. atomizing microwave plasma CVD in a liquid phase source prepares the method for film, and concrete steps are as follows:
(1) preparation in liquid phase atomizing source
With thin-film material by the stoichiometric ratio of its composition carry out raw material calculating and accurately weigh after, select soluble salt to be system pleurodiaphragmatic in terspace material, be dissolved in the different solvents respectively according to the deliquescent difference of its salt, the homogeneous solution of each self-forming 0.3mol/L-1.0mol/L, then that above solution is neutral by the acid back of elder generation, last alkaline order adds mixing respectively; Be modulated into the aerosolizable even colloidal sol or the solution of 0.06mol/L-0.2mol/L concentration at last, as liquid phase atomizing source;
(2) plasma exciatiaon chemical reaction process
Above liquid phase colloidal sol or solution are carried out ultrasonic atomizatio, with atomization gas with in the 10-30ml/min flow feeding reaction chamber, under the microwave generator effect, in reaction chamber, inspired the high enthalpy microwave plasma of high temperature, with the little droplet that imports, meet the thin-film material stoichiometric ratio, at first gasification, and then take place to decompose and ionization, ion formed; These are through ionized ion, electronics, and neutral molecule, and activity is very high each other, chemical reaction takes place, when breaking away from the pyritous plasma slab under the effect of air-flow, owing to high thermograde occurs, cold soon rapidly, make gaseous product form the solid product particle rapidly, be deposited on substrate;
(3) forming process of film
Through the solid phase particles that above chemical gas phase reaction generates, under the drive of air-flow, can clash into, and part is under deposition on the substrate with substrate base; Substrate temperature can be controlled by well heater, in the sedimentary initial stage, substrate temperature is controlled at 500-650 ℃, and this low relatively temperature helps depositing the nucleation of solid phase particles on substrate of getting off; Along with the carrying out of deposition process, in the sedimentary middle and later periods, temperature is controlled between 650-850 ℃, this high relatively depositing temperature helps growth for Thin Film; Reach the crystallinity film that use properties requires.
2. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that described soluble salt is inorganic salt or organic salt.
3. a kind of liquid phase as claimed in claim 1 or 2 source atomizing microwave plasma CVD prepares the method for film, when it is characterized in that described solution is polycomponent solution, need introducing citric acid, ethylene glycol easily to form the complexing agent or the cross-linking agent solution of complex structure, need introduce ethylenediamine tetraacetic acid (EDTA) (EDTA) again to the solution of slant acidity and make the abundant complexing of each component of above mixing solutions and be transformed into stable sols, to increase liquid phase homogeneity and stability.
4. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that described substrate is arranged with well heater and micromotor, well heater may command underlayer temperature, micromotor can make substrate rotate with 2 rev/mins speed, makes the thin-film material homogenizing that is deposited on the substrate.
5. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that the deposition pressure in the described reaction chamber maintains between the 100-600Pa by vacuum pump.
6. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that the various processing parameters of described film-forming process can be by computer realization automatization control and monitoring.
7. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that described the 3rd step, can directly form crystallization thin film to general material by control, to the relatively more difficult thin-film material of synthetic phase composite, can be after deposition reaction finishes, put into further anneal of heat treatment furnace together with substrate, so that the material crystallization is complete.
8. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, it is characterized in that described second step, with the argon gas of easily ionizable or be under the drive of supporting gas directly, atomization gas is imported in the reaction chamber with the reaction gas.
9. a kind of liquid phase as claimed in claim 1 source atomizing microwave plasma CVD prepares the method for film, the colloidal sol or the solution that it is characterized in that described second step are inserted in the glass volumetric flask that is complementary with spraying gun, be placed on the ultrasonic atomizer, providing chemical reaction source, spraying gun power with the liquid phase atomizing is 50-100W.
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| CN101730373B (en) * | 2008-11-03 | 2012-09-05 | 北京坚润表面材料研究所 | Method and device for forming new materials by discharge of fog gas |
| TWI579405B (en) * | 2012-11-15 | 2017-04-21 | 財團法人工業技術研究院 | Plasma deposition apparatus |
| CN103433499B (en) * | 2013-08-27 | 2015-08-12 | 湖南航天工业总公司 | A kind of ultrasonic atomizatio preparation facilities of globular metallic powder and preparation method |
| CN103590022A (en) * | 2013-11-27 | 2014-02-19 | 昆明理工大学 | Method for making film through ultrasonic atomization-microwave pyrolysis |
| CN106119809B (en) * | 2016-05-04 | 2018-10-30 | 上海大学 | High throughput combination prepares VO2The device and method of film |
| CN108054341B (en) * | 2017-12-22 | 2020-09-15 | 湖南工业大学 | Preparation method of graphene/silicon-carbon composite material |
| CN109056066A (en) * | 2018-09-05 | 2018-12-21 | 南京大学 | A kind of system of ultrasonic wave added mist phase transport chemical vapor deposition growing gallium oxide |
| CN110396675B (en) * | 2019-07-10 | 2021-12-31 | 中国科学院电工研究所 | Preparation method of plasma enhanced chemical vapor deposition metal film |
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