CN107630203B - A kind of method of normal pressure cold plasma deposited metal simple substance membrane - Google Patents
A kind of method of normal pressure cold plasma deposited metal simple substance membrane Download PDFInfo
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- CN107630203B CN107630203B CN201710863539.3A CN201710863539A CN107630203B CN 107630203 B CN107630203 B CN 107630203B CN 201710863539 A CN201710863539 A CN 201710863539A CN 107630203 B CN107630203 B CN 107630203B
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Abstract
The invention discloses a kind of methods of normal pressure cold plasma deposited metal simple substance membrane, comprising the following steps: Step 1: mixed gas is excited, ionization generates normal pressure cold plasma, and normal pressure cold plasma forms plasma flare in the cavity of nozzle；Step 2: entering in the cavity of nozzle after metal compound solution atomization；Step 3: plasma flare is had an effect with droplet under the circular protection of protective gas, solvent evaporation in droplet, the metallic compound in droplet, which is reduced into metallic and is ejected into deposition on matrix, forms continuous metal simple-substance film.The present invention can deposited metal simple substance membrane under normal pressure, reaction temperature is low, is suitable for thermal sensitivity matrix, and expand the application range of method so that matrix size be made not limited by space without vacuum or closed settling chamber；Metal simple-substance property of thin film prepared by the present invention is stablized, and without being post-processed, so as to shorten process flow, improves production efficiency.
Description
Technical field
The invention belongs to technical field of thin film deposition, and in particular to a kind of normal pressure cold plasma deposited metal simple substance membrane
Method.
Background technique
When being reduced in size to the micro-scale moved close to quantization of metallic film material, can show many completely new
Physical phenomenon, facilitates microelectronic component and system is further miniaturized, and be combined with each other can structure for different metal materials
At the material with complex system with excellent characteristics, has in fields such as material science, electromagnetism and life sciences and widely answer
Use prospect.Currently, metallic film preparation main method have physical vaporous deposition (PVD), chemical vapour deposition technique (CVD),
Electrodeposition process and chemical deposition.A large amount of chemical waste fluids can be generated in the preparation process of electrodeposition process and chemical deposition, to ring
Border is harmful.And the precursor reagent of traditional PVD and CVD are mostly solid or gas, select type less；The also Primordial Qi used
Body is mostly hydrogen, inflammable and explosive；Reaction temperature is high when preparing metallic film, and matrix easy to damage simultaneously leads to film oxidation, so often
It often needs under vacuum conditions or is carried out in closed settling chamber, greatly limit the matrix size of deposition in this way.In addition, mistake
The metal thin-film properties that high reaction temperature is prepared are not sufficiently stable, it is also necessary to be made annealing treatment, to increase post-processing
Technique reduces preparation efficiency.
Plasma vapor deposition processes are to generate reactant by chemical reaction solid using plasma as energy source
The method that phase particle deposition obtains solid film on matrix.The whole system of plasma can be divided into cold etc. by system temperature
Gas ions and hot plasma.The energy of particle is generally several to more than ten electron-volt in cold plasma, bulk temperature
It is low, material surface is pertained only to, substrate performance is not influenced.Plasma can be divided into low pressure and often according to the difference of reaction pressure
Press plasma.Normal pressure cold plasma is not due to needing vacuum, the advantages that easy to operate and deposition velocity is fast, becomes preparation
The research hotspot of film.Currently, normal pressure cold plasma technology has been applied to prepare on oxidation film, but thin preparing metal simple-substance
There is not been reported for research in terms of film.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of normal pressure it is cold it is equal from
The method of daughter deposited metal simple substance membrane.This method, around protection plasma flare, makes metal compound using protective gas
Object is reduced to metallic in the state of with air exclusion and is ejected on matrix, then moves plasma torch and drives nozzle
Jet port deposit to form continuous metal simple-substance film with respect to matrix rapid horizontal；This method can deposit under normal pressure
Metal simple-substance film, reaction temperature is low, is suitable for thermal sensitivity matrix, and be not necessarily to vacuum or closed settling chamber, to make to deposit
Matrix size do not limited by space, expand the application range of method, and the metal simple-substance film of this method preparation
Matter is stablized, without being post-processed.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of normal pressure cold plasma deposited metal
The method of simple substance membrane, which comprises the following steps:
Step 1: mixed gas is inputted in plasma torch, mixed gas ionizes under the discharge excitation of electrode, produces
Raw normal pressure cold plasma, the normal pressure cold plasma form plasma flare in the cavity of nozzle；
Step 2: metallic compound, which is dissolved in solvent, is configured to metal compound solution, then by metal compound solution
It is atomized into droplet, and enters step droplet in the cavity of nozzle described in one；
Step 3: under the circular protection of protective gas, described in plasma flare described in step 1 and step 2
Droplet is had an effect, the solvent evaporation in droplet, and the metallic compound in droplet is reduced into metallic and is ejected on matrix,
Mobile plasma torch simultaneously drives the jet port of nozzle to move horizontally with respect to matrix, metal particle deposition company of being formed on matrix
Continuous metal simple-substance film.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 1
State the protective gas channel for offering the droplet channel being connected to cavity on the side wall of nozzle and being connected to jet port, the droplet
Channel is passed through the droplet for being atomized and being formed, and the protective gas channel is passed through the protective gas around protection plasma flare.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 1
Mixed gas is stated to be mixed with nitrogen equipressure by ammonia or mixed by ammonia and argon gas equipressure；The mixed gas
Pressure is 0.25MPa~0.80MPa.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that the gaseous mixture
The volume content of ammonia is 1%~30% in body.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 1
Stating normal pressure cold plasma is normal pressure jet stream cold plasma or normal-pressure radio-frequency cold plasma.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 2
Stating metallic compound is metal salt.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 2
The mode for stating atomization is pneumatic nebulization or ultrasonic atomization；Using inert gas or nitrogen as power gas when the pneumatic nebulization
Body, the flow of the power gas are 2L/min~10L/min；The frequency of the ultrasonic atomization is 1.2MHz~2.5MHz.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 3
Stating protective gas is argon gas or nitrogen, and the flow of the protective gas is 8L/min~30L/min.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 3
Stating matrix is stainless steel band, silver-colored band, copper bar, aluminum strip, ceramics, glass, plastics, nickel strap or silicon wafer.
A kind of method of above-mentioned normal pressure cold plasma deposited metal simple substance membrane, which is characterized in that institute in step 3
Stating the distance between jet port and matrix of nozzle is 2mm~18mm, and the mobile speed of relative level is 5m/min~20m/
min。
Compared with the prior art, the present invention has the following advantages:
1, metallic compound is reduced to metallic under normal pressure cold plasma effect by the present invention, first using guarantor
It protects gas-circulating and protects plasma flare, metallic compound is made to be reduced to metallic injection in the state of with air exclusion
Onto matrix, avoid the oxygen in air to the oxidation of metallic；Then the spray that plasma torch drives nozzle is moved
Loophole reduces the temperature rise of saltation point with respect to matrix rapid horizontal, when the oxygen in the film and air of deposition being avoided to contact
Occur oxidation reaction, thus the present invention can direct deposited metal simple substance membrane under normal pressure, and without vacuum or closed heavy
Product room expands the application range of method so that the matrix size of deposition be made not limited by space.
2, the reaction temperature in the present invention is lower, is suitable for the metal simple-substance film deposition of thermal sensitivity matrix surface, expands
The range of choice of basis material；And the metal simple-substance property of thin film prepared is stablized, and without annealing, shortens technique stream
Journey improves production efficiency.
3, the present invention is reacted again after being atomized metal compound solution using atomization technique, and selected metallic compound is simultaneously
Not necessarily there is preferable volatility, as long as can be dissolved in the solvent for being easy atomization, to reduce to reactant
The requirement of volatility and stability expands the range of choice of reactant.
4, hydrogen is replaced with ammonia in mixed gas used in normal pressure cold plasma of the invention, ammonia is heated easily to be decomposed
Nitrogen and hydrogen are generated, metallic compound is participated in and is converted to the reduction reaction of metallic, and can get same function and effect；
Ammonia has specific stimulation smell simultaneously, if leakage occurs can find there is higher safety in actual production in time
Coefficient, and the preparation of ammonia is easier than hydrogen, cost is lower relative to hydrogen, can reduce and be produced into while safety in production
This.
Invention is further described in detail with reference to the accompanying drawings and examples.
Detailed description of the invention
Fig. 1 is the schematic device of normal pressure cold plasma deposited metal simple substance membrane of the invention.
Fig. 2 is that the XPS for the Copper thin film that the embodiment of the present invention 1 deposits composes scanning figure entirely.
Fig. 3 is the Cu2p spectrogram for the Copper thin film that the embodiment of the present invention 1 deposits.
Fig. 4 is the CuLMM Auger spectrogram for the Copper thin film that the embodiment of the present invention 1 deposits.
Description of symbols:
1-the first admission line；2-the second admission line；3-the first valve；
4-the second valve；5-gas proportion mixing devices；6-gas transport pipelines；
7-plasma electrical sources；8-electric wires；9-electrodes；
10-plasma torch；11-nozzles；12-cavitys；
13-jet ports；14-droplet channels；15-droplet transport pipelines；
16-spray chambers；17-third valves；18-third admission lines
19-protective gas channels；20-the four valve；21-the four admission line；
22-pedestals.
Specific embodiment
As shown in Figure 1, normal pressure cold plasma deposited metal simple substance used in 1~embodiment of the embodiment of the present invention 9 is thin
The device of film includes gas proportion mixing device 5, plasma torch 10 and spray chamber 16, and the gas proportion mixing device 5 has
Two air inlets and a gas outlet, one of air inlet are connect with the first admission line 1, are arranged on the first admission line 1
There is the first valve 3, another air inlet is connect with the second admission line 2, the second valve 4 is provided on the second admission line 2,
The gas outlet of gas proportion mixing device 5 is connect by gas transport pipeline 6 with plasma torch 10, the plasma torch
Electrode 9 is provided in 10, the electrode 9 is connect by electric wire 8 with plasma electrical source 7, the end of the plasma torch 10
Mouth is provided with nozzle 11, and the nozzle 11 includes cavity 12 and jet port 13, and the underface of the jet port 13, which is provided with, to be used for
The pedestal 22 of fixing base, offer on the side wall of the cavity 12 the droplet channel 14 being connected to cavity 12 and with jet port 13
The protective gas channel 19 of connection, the droplet channel 14 is exported by the droplet of droplet transport pipeline 15 and spray chamber 16 to be connected
It connects, the air inlet of the spray chamber 16 is connect with third admission line 18, is provided with third valve on the third admission line 18
Door 17, the protective gas channel 19 is connect with the 4th admission line 21, is provided with the 4th valve on the 4th admission line 21
Door 20.
Embodiment 1
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 8:92, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.25MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: copper nitrate is configured to the solution that concentration is 150g/L, it is placed in spray chamber 16, opens third valve
17, nitrogen is entered in spray chamber 16 by third admission line 18, and copper nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the nitrogen is 3L/
min；
Step 3: opening the 4th valve 20, nitrogen enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With, solvent in droplet evaporation, the copper nitrate in droplet is reduced into copper metal particle and is ejected on stainless steel band, it is mobile etc. from
Daughter spray gun 10 simultaneously drives the jet port 13 of nozzle 11 to move horizontally with respect to stainless steel band, and copper metal particle is deposited on stainless steel band
It is upper to form continuous Copper thin film；The flow of the nitrogen is 10L/min；Between the jet port 13 and stainless steel band of the nozzle 11
Distance be 3mm, relative level movement speed be 6m/min.
Using the Copper thin film of the present embodiment deposition as sample, sample is detected using X-ray photoelectron spectroscopy (XPS)
(excitaton source Al), as a result as shown in Figure 2, Figure 3 and Figure 4.
Fig. 2 is the full spectrum scanning figure of the Copper thin film of the present embodiment deposition, and as seen from Figure 2, complete compose occurs in scanning figure
The spectral peak of C1s, O1s, CuLMM and Cu2p can determine and contain three kinds of carbon, oxygen and copper elements in sample；Due to the intensity of spectral peak
The content of corresponding element is directly proportional, can speculate that the content of copper in sample is most, the content of oxygen element and carbon
It is less.Sample is both exposed in air after deposition is formed and in detection process, will receive pollution, the surface of sample is often adsorbed
There are a small amount of carbon and oxygen, therefore will appear carbon and the weaker spectral peak of oxygen in Fig. 2.
Fig. 3 is that the Cu2p spectrogram of the Copper thin film of the present embodiment deposition occurs in Cu2p spectrogram as seen from Figure 3
The spectral peak of Cu2p1/2 and Cu2p3/2, but peak is swashed without occurring shaking, it can determine in sample without cupric.
Fig. 4 is the CuLMM Auger spectrogram of the Copper thin film of the present embodiment deposition, as seen from Figure 4, in conjunction with can be
Occurs spectral peak at 568.1eV, control combines energy handbook that can determine that the chemical state of copper in sample is zerovalent copper, i.e. sample
Copper thin film is copper simple substance film.
Embodiment 2
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and argon gas respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 8:92, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.35MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal-pressure radio-frequency cold
Plasma, the normal-pressure radio-frequency cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: will be bis- (hexafluoroacetylacetone) close copper dissolution be configured in ethyl acetate concentration be 1.4mol/L it is molten
Liquid is placed in spray chamber 16, closes third valve 17, then by ultrasonic wave that frequency is 1.2MHz by bis- (hexafluoroacetylacetonates
Ketone) it closes copper solution and is atomized into droplet, droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；
Step 3: opening the 4th valve 20, nitrogen enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and bis- (hexafluoroacetylacetones) conjunction copper in droplet is reduced into copper metal particle and is ejected into glass
On, mobile plasma torch 10 simultaneously drives the jet port 13 of nozzle 11 mobile relative to glass horizontal, and copper metal particle is deposited on
Continuous Copper thin film is formed on glass；The flow of the nitrogen is 30L/min；Between the jet port 13 and glass of the nozzle 11
Distance be 2mm, relative level movement speed be 9m/min.
Embodiment 3
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and argon gas respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 3:7, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.80MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: zinc nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, opens third valve
17, nitrogen is entered in spray chamber 16 by third admission line 18, and zinc nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the nitrogen is 10L/
min；
Step 3: opening the 4th valve 20, argon gas enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the zinc nitrate in droplet is reduced into zinc metallic and is ejected on ceramics, mobile plasma
Spray gun 10 simultaneously drives the ceramics relatively of jet port 13 of nozzle 11 to move horizontally, and zinc metal particle deposition is formed continuously on ceramics
Zinc film；The flow of the argon gas is 15L/min；The distance between jet port 13 and ceramics of the nozzle 11 are 18mm, phase
It is 5m/min to horizontal movement velocity.
Embodiment 4
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 3:7, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.80MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal-pressure radio-frequency cold
Plasma, the normal-pressure radio-frequency cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: zinc nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, opens third valve
17, nitrogen is entered in spray chamber 16 by third admission line 18, and zinc nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the nitrogen is 2L/
min；
Step 3: opening the 4th valve 20, nitrogen enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the zinc nitrate in droplet is reduced into zinc metallic and is ejected on copper bar, mobile plasma
Spray gun 10 simultaneously drives the jet port 13 of nozzle 11 to move horizontally with respect to copper bar, and zinc metal particle deposition is formed continuously on copper bar
Zinc film；The flow of the nitrogen is 20L/min；The distance between jet port 13 and copper bar of the nozzle 11 are 10mm, phase
It is 6m/min to horizontal movement velocity.
Embodiment 5
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 1:99, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.35MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: ferric nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, closes third valve
17, iron nitrate solution is then atomized by droplet by the ultrasonic wave that frequency is 2.5MHz, droplet passes through droplet transport pipeline 15
Droplet channel 14 is transported to subsequently into cavity 12；
Step 3: opening the 4th valve 20, nitrogen enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the ferric nitrate in droplet is reduced on ferrous metal particle spraying to aluminum strip, mobile plasma
Spray gun 10 simultaneously drives the jet port 13 of nozzle 11 to move horizontally with respect to aluminum strip, and it is continuous that ferrous metal particle deposits formation on aluminum strip
Iron thin film；The flow of the nitrogen is 8L/min；The distance between jet port 13 and aluminum strip of the nozzle 11 are 6mm, relatively
Horizontal movement velocity is 20m/min.
Embodiment 6
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and argon gas respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 1:99, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.50MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal-pressure radio-frequency cold
Plasma, the normal-pressure radio-frequency cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: will be bis- (hexafluoroacetylacetone) close copper be dissolved in ethyl acetate be configured to concentration be 1.4mol/L solution,
It is placed in spray chamber 16, closes third valve 17, it then will be bis- (hexafluoroacetylacetone) by the ultrasonic wave that frequency is 1.7MHz
It closes copper solution and is atomized into droplet, droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；
Step 3: opening the 4th valve 20, argon gas enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and bis- (hexafluoroacetylacetones) conjunction copper in droplet is reduced into copper metal particle and is ejected into silver-colored band
On, mobile plasma torch 10 simultaneously drives the relatively silver-colored band of the jet port 13 of nozzle 11 to move horizontally, and copper metal particle is deposited on
Silver takes to form continuous Copper thin film；The flow of the argon gas is 20L/min；Between the jet port 13 and silver band of the nozzle 11
Distance be 4mm, relative level movement speed be 12m/min.
Embodiment 7
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 1:9, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.50MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: ferric nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, opens third valve
17, argon gas is entered in spray chamber 16 by third admission line 18, and iron nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the argon gas is 3L/
min；
Step 3: opening the 4th valve 20, nitrogen enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the ferric nitrate in droplet is reduced on ferrous metal particle spraying to plastics, mobile plasma
Spray gun 10 simultaneously drives 13 opposed plastic of jet port of nozzle 11 to move horizontally, and ferrous metal particle deposition is formed continuously on plastics
Iron thin film；The flow of the nitrogen is 15L/min；The distance between jet port 13 and plastics of the nozzle 11 are 10mm, phase
It is 16m/min to horizontal movement velocity.
Embodiment 8
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 2:8, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.50MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: zinc nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, opens third valve
17, argon gas is entered in spray chamber 16 by third admission line 18, and zinc nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the argon gas is 10L/
min；
Step 3: opening the 4th valve 20, argon gas enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the zinc nitrate in droplet is reduced into zinc metallic and is ejected on nickel strap, mobile plasma
Spray gun 10 simultaneously drives the jet port 13 of nozzle 11 to move horizontally with respect to nickel strap, and zinc metal particle deposition is formed continuously on nickel strap
Zinc film；The flow of the argon gas is 30L/min；The distance between jet port 13 and nickel strap of the nozzle 11 are 5mm, relatively
Horizontal movement velocity is 10m/min.
Embodiment 9
The present embodiment the following steps are included:
Step 1: open the first valve 3 and the second valve 4, make ammonia and nitrogen respectively via the first admission line 1 and the
Two admission lines 2 enter in gas proportion mixing device 5, and carry out isobaric mixing according to the volume ratio of 6:94, and forming pressure is
Then mixed gas is delivered in plasma torch 10 by gas transport pipeline 6, is adjusted by the mixed gas of 0.35MPa
The output power of plasma electrical source 7 is 400W, and mixed gas ionizes under the discharge excitation of electrode 9, generates normal jet flow cold
Plasma, the normal pressure jet stream cold plasma form plasma flare in the cavity 12 of nozzle 11；
Step 2: copper nitrate is configured to the solution that concentration is 100g/L, it is placed in spray chamber 16, opens third valve
17, argon gas is entered in spray chamber 16 by third admission line 18, and copper nitrate solution is atomized into droplet as power gas,
Droplet is transported to droplet channel 14 subsequently into cavity 12 by droplet transport pipeline 15；The flow of the argon gas is 2L/
min；
Step 3: opening the 4th valve 20, argon gas enters protective gas channel 19 by the 4th admission line 21 and is spraying
Around protection plasma flare at loophole 13, plasma flare described in step 1 is made with droplet described in step 2
With the solvent in droplet evaporates, and the copper nitrate in droplet is reduced into copper metal particle and is ejected on silicon wafer, mobile plasma
Spray gun 10 simultaneously drives the jet port 13 of nozzle 11 mobile relative to silicon wafer horizontal, and copper metal particle is deposited on silicon wafer and is formed continuously
Copper thin film；The flow of the argon gas is 8L/min；The distance between jet port 13 and silicon wafer of the nozzle 11 are 3mm, relatively
Horizontal movement velocity is 10m/min.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope in.
Claims (10)
1. a kind of method of normal pressure cold plasma deposited metal simple substance membrane, which comprises the following steps:
Step 1: mixed gas is inputted in plasma torch (10), mixed gas is electric under the discharge excitation of electrode (9)
From generation normal pressure cold plasma, the normal pressure cold plasma forms plasma light in the cavity (12) of nozzle (11)
Flame；
Step 2: metallic compound, which is dissolved in solvent, is configured to metal compound solution, then metal compound solution is atomized
At droplet, and enter step droplet in the cavity (12) of nozzle described in one (11)；
Step 3: under the circular protection of protective gas, droplet described in plasma flare described in step 1 and step 2
It has an effect, the solvent in droplet evaporates, and the metallic compound in droplet is reduced into metallic and is ejected on matrix, mobile
Plasma torch (10) simultaneously drives the jet port (13) of nozzle (11) to move horizontally with respect to matrix, and metal particle deposition is in matrix
It is upper to form continuous metal simple-substance film.
2. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Offered on the side wall of nozzle described in step 1 (11) the droplet channel (14) being connected to cavity (12) and with jet port (13)
The protective gas channel (19) of connection, the droplet channel (14) are passed through the droplet for being atomized and being formed, the protective gas channel
(19) it is passed through the protective gas around protection plasma flare.
3. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Mixed gas described in step 1 is mixed by ammonia with nitrogen equipressure or is mixed by ammonia and argon gas equipressure；It is described
The pressure of mixed gas is 0.25MPa~0.80MPa.
4. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 3, which is characterized in that
The volume content of ammonia is 1%~30% in the mixed gas.
5. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Normal pressure cold plasma described in step 1 is normal pressure jet stream cold plasma or normal-pressure radio-frequency cold plasma.
6. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Metallic compound described in step 2 is metal salt.
7. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
The mode of atomization described in step 2 is pneumatic nebulization or ultrasonic atomization；Made when the pneumatic nebulization with inert gas or nitrogen
For power gas, the flow of the power gas is 2L/min~10L/min；The frequency of the ultrasonic atomization be 1.2MHz~
2.5MHz。
8. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Protective gas described in step 3 is argon gas or nitrogen, and the flow of the protective gas is 8L/min~30L/min.
9. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, which is characterized in that
Matrix described in step 3 is stainless steel band, silver-colored band, copper bar, aluminum strip, ceramics, glass, plastics, nickel strap or silicon wafer.
10. a kind of method of normal pressure cold plasma deposited metal simple substance membrane according to claim 1, feature exist
In the distance between the jet port (13) of nozzle described in step 3 (11) and matrix are 2mm~18mm, relative level movement
Speed is 5m/min~20m/min.
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| CN108611623B (en) * | 2018-06-28 | 2020-07-31 | 中国科学院电工研究所 | Spraying coating device and method for inhibiting secondary electron yield of solid dielectric material |
| CN110787661A (en) * | 2018-08-01 | 2020-02-14 | 台鉅生技股份有限公司 | Polymer-collagen composite membrane and method for producing same |
| CN109267037A (en) * | 2018-11-21 | 2019-01-25 | 新疆大学 | Atmospheric plasma enhances chemical vapor deposition method and the equipment using this method |
| CN110295340B (en) * | 2019-07-15 | 2021-09-03 | 何舒扬 | Crack monitoring sensor based on plasma spraying and preparation and monitoring methods thereof |
| KR102180979B1 (en) * | 2019-08-19 | 2020-11-19 | 참엔지니어링(주) | Processing apparatus and method |
| US20230032817A1 (en) * | 2019-09-10 | 2023-02-02 | Ucl Business Ltd | Plasma jet deposition process |
| DE102021107153A1 (en) | 2021-03-23 | 2022-09-29 | Plasmatreat Gmbh | METHOD OF COATING A SURFACE OF A SUBSTRATE WITH A CONTINUOUS METAL LAYER |
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