CN110274803A - Can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method - Google Patents
Can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method Download PDFInfo
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- CN110274803A CN110274803A CN201910460855.5A CN201910460855A CN110274803A CN 110274803 A CN110274803 A CN 110274803A CN 201910460855 A CN201910460855 A CN 201910460855A CN 110274803 A CN110274803 A CN 110274803A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/84—Systems specially adapted for particular applications
- G01N21/8422—Investigating thin films, e.g. matrix isolation method
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
- G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
Abstract
The present invention relates to the preparation of thin-film material and application field, it is specifically a kind of can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, realize the uniform nanometer grade thickness thin-film material of thickness efficient control prepare.This method uses the basic principle of rotating centrifugal film-forming method, using printing head or syringe needle with micro-aperture on the basis of matrix rotating device, under conditions of constant film forming liquid pressure and controlled motion track, a certain amount of film forming liquid is ejected into the film forming matrix surface being rotating with given pace in the form of fine fluid column, thickness, shape and the controllable uniform liquid film of area are formed, and then obtains the membrane material of solid by control condition of cure.The efficient accurate control preparation of the uniform nanometer grade thickness thin-film material of thickness may be implemented in this method, can be widely applied to the technical fields such as photoelectric device, energy storage device, safeguard function coating, catalysis material, composite material.
Description
Technical field
The present invention relates to the preparation of thin-film material and application field, it is specifically a kind of can accuracy controlling nanometer grade thickness film
The film-forming method of film forming thickness and area.
Background technique
Flexible large area even thin-film material can be widely applied to photoelectric device, energy storage device, safeguard function and apply
Layer catalyzes and synthesizes, the technical fields such as composite material, and realizes the efficient control of the uniform nanometer grade thickness thin-film material of thickness
System preparation is the critical process basis for realizing above-mentioned application.Currently, industrial common nanometer grade thickness thin-film material prepares skill
Art mainly has vapor deposition, magnetron sputtering, spraying, spin coating, blade coating, inkjet printing etc..Wherein, vapor deposition and magnetron sputtering may be implemented
The material of even thickness deposits, but its is complicated for operation, and equipment cost is high, and the requirement to target is high.Spin coating and inkjet printing are made
It is small with area, low efficiency, therefore can not large-area preparation of thin film material, and large-area uniformity is poor；Spraying and doctor blade process
The preparation of large area film material may be implemented, but be generally difficult to prepare the thin-film material of nanometer grade thickness.
Publication No.: the Chinese invention patent application of CN108568926A, open one kind efficiently prepare highly directional, high-densit
The method of two-dimensional material film, for this method using the smooth round tube of inner surface as casting die, mold high speed is circumferentially square
To pouring into the solution (at film liquid) containing two-dimensional material in mold when rotation, two-dimensional material is assembled into using centrifugal force thin
Film.The available high orientation of this method, high-densit two-dimensional material film.But the charging side that this direct formation of film at surface liquid pours into
Method accurately cannot control and adjust film-forming region, it is also difficult to which the uniformity for controlling film forming, therefore, it is difficult to prepare uniform nanometer
The thin-film material of grade thickness.Publication No.: the Chinese invention patent application of CN109177010A, on the basis of above-mentioned film-forming method
On, it will be changed to atomizing spraying at the feeding manner of film liquid, micron-sized drop is melted by the liquid mist that will form a film and is rotating it
It is deposited on surface, can effectively prepare the membrane material with nanometer grade thickness；But due to liquid drop speed in atomizer (atomizing) cone
Unevenly, the thickness of gained thin-film material is still difficult to uniformity over a large area；Simultaneously because the needs of atomization, the party
The film forming liquid that method can utilize needs extremely low viscosity, and more demanding to the dispersibility of film forming matter in a solvent；In addition,
This method is also not suitable for being film-made using flammable organic solvent solution, and the danger such as detonation easily occur for the drop being otherwise atomized.
In conclusion the efficient control preparation in order to more preferably realize the uniform nanometer grade thickness thin-film material of thickness,
It needs to optimize existing centrifugation film-forming method.
Summary of the invention
The purpose of the present invention is to provide it is a kind of can accuracy controlling nanometer grade thickness forming thin film thickness and area film
Method realizes the efficient control preparation of the uniform nanometer grade thickness thin-film material of thickness.
The technical scheme is that
It is a kind of can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, include the following steps:
(1) membrane equipment is sprayed using rotating centrifugal, is in film forming used film forming matrix and stablizes rotation status；
(2) spray head with hole or syringe needle are used, in the case where constant film forming liquid pressure, by film forming matter preparation
Film forming liquid is ejected into the film forming matrix surface being rotating in the form of fluid column, makes film forming liquid being total in shearing force and centrifugal force
It is cyclic annular that uniform fillet is elongated under same-action；
(3) in order to which the film-forming region for obtaining different in width utilizes program while spray head or syringe needle injection film forming liquid
The mechanical device of control translates spray head or syringe needle feed inlet along with the direction of roller rotation axis horizontal；Spray head or syringe needle translation
Distance be to be used to the width of film-forming region, according to film need to control spray head or syringe needle the both ends of translation distance it
Between move back and forth, spray head or syringe needle are in stable injection state always in translation motion；By aforesaid operations, rotation at
Film matrix surface, forms the continuous liquid film of setting width, and the above process is defined as a fluid injection operating process；
(4) curing process, curing process process are carried out to liquid film while completing a fluid injection operating process or later
The middle rotation status for keeping film forming matrix is constant, that is, saves film forming matrix and be in stable centrifugal force field, complete in the liquid film
One-pass film-forming operation is completed after solidification；
(5) it after completing one-pass film-forming operation, is required according to film or device manufacture requires, it is above once or twice to repeat
Above-mentioned Film forming operations process is changed to the film liquid of other materials or changes parameters of preparation, above once or twice to execute
Film forming operations process is stated, to obtain the thin-film material or two layers or more composite film material being constituted of heterogeneity of different-thickness；
(6) after completing above-mentioned film operation, according to resulting devices or application requirement, gained thin-film material and film forming matrix are total
In the case where with allowing using or film itself mechanical property, from the removing of film forming matrix surface and independent utility.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, in step (1), rotation
Centrifugal spraying membrane equipment includes: rotating electric machine, rotating cylinder, optical wave heating pipe, syringe needle mobile device, form a film matrix, syringe needle,
Specific structure is as follows:
Rotating electric machine extends to rotating cylinder by the rotation horizontally disposed rotating cylinder of axis connection, optical wave heating pipe level
Interior, the syringe needle of syringe needle mobile device one end is corresponding with the film forming base inner surface on the inside of rotating cylinder, and the matrix that forms a film is with rotation
Roller rotation, syringe needle mobile device drive syringe needle to translate along with the direction of rotary drum rotating axis level, and film forming liquid passes through
The syringe needle injection film forming matrix surface of syringe needle mobile device.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, in step (1), rotation
Centrifugal spraying film specific operation process include:
I. film forming basis material is selected according to application demand, the film forming matrix is organic or inorganic membrane material flexible or piece
Material, including but not limited to various resin films, resin compounded film, metal film or non-metallic film；
II. the matrix to form a film will be needed to be tightly attached to rotating cylinder inner wall, patch matrix mode uses but is not limited only to directly paste
Matrix plus sticker matrix or liquid feeding show consideration for matrix；Matrix is directly pasted, i.e., matrix curling is directly fitted in into rotating cylinder inner wall
On；Add bond paper facing, i.e., glue is added between matrix and rotating cylinder inner wall and is bonded；Liquid feeding shows consideration for matrix, i.e., in matrix and
Liquid is added between rotating cylinder inner wall, is bonded matrix and rotating cylinder inner wall using the capillarity of liquid；
III. film forming matrix rotation, the centrifugation for obtaining film forming substrate surface position because of rotation are driven by mechanical device
Acceleration is in the range of 0.1g~500000g, and g is acceleration of gravity, numerical value 9.8m/s2, and keep stable.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, in step (2), spray head
Or the pore diameter range of syringe needle is 1 μm~10cm, the range of film forming liquid pressure is 10Pa~100MPa, and the matrix that forms a film is because of centrifugal rotary
Then the centrifugal acceleration range obtained is 0.1g~500000g, g is acceleration of gravity, numerical value 9.8m/s2。
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, film forming matter includes each
Kind high-molecular organic material, two-dimensional material, one-dimensional material or zero dimension material；Wherein, organic polymer film includes but is not limited to
Polyimides, polyurethane, polyethylene, epoxy resin, natural rubber, PEDOT:PSS or silicon rubber；Two-dimensional material includes but unlimited
In graphene, boron nitride, Transition-metal dichalcogenide, two-dimentional transition metal carbide, two-dimentional transition metal nitride or black
Phosphorus；One-dimensional material includes carbon nanotube, silver nanowires, copper nano-wire or nanofiber；Zero dimension material includes but is not limited to that silicon is received
Rice grain, nano SiO 2 particle, Titanium dioxide nanoparticle, carbon black or fullerene.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, film forming matter is configured to
Solution or suspension fluid state, solvent for use include various inorganic or organic solvent, or may participate in the active organic of film forming
Diluent；Wherein, inorganic solvent includes but is not limited to water, ionic liquid, acetic acid, sulfuric acid or liquefied ammonia；Organic solvent includes but not
It is limited to ethyl alcohol, propyl alcohol, acetone, benzene, chlorine benzene,toluene,xylene, acetonitrile, ether or chloroform；Reactive diluent includes but is not limited to
Alkylidene glycidol ether, neodecanoic acid glycidol rouge, butyl glycidyl ether, toluene glycidol ether, castor oil shrink more
Glycerin ether, hydroxyethyl methacrylate or hexanediyl ester.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, in step (3), liquid film
Thickness range be 50nm~5000 μm.
It is described can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, in step (4), solidification
Processing method include but is not limited to heating, drying, reduction vaporization, photocuring, heat cure, injection curing agent curing mode in one
Kind or two or more combinations；One-pass film-forming operation gained thin-film material thickness range be 1nm~500 μm, at film
Range of surface roughness is 1nm~20nm.
Design philosophy of the invention is:
The present invention is the basic principle based on rotating centrifugal film-forming method, while utilizing the new of rotating cylinder component development
Nano film material preparation method.The present invention is film-made used film forming matrix and is at certain speed by mechanical device drive
Rotation status forms uniform centrifugal force field.
The present invention is on the basis of matrix rotating device, using printing head or syringe needle with micro-aperture, constant
In the case where film forming liquid pressure and controlled motion track, a certain amount of film forming liquid is ejected into the form of fine fluid column with
The film forming matrix surface that given pace is rotating is elongated film forming liquid under shearing force and the collective effect of centrifugal force
It is cyclic annular at uniform fillet, thickness, shape and the controllable uniform liquid film of area are formed, and then consolidated by controlling condition of cure
The membrane material of body.The efficient accurate control preparation of the uniform nanometer grade thickness thin-film material of thickness may be implemented in this method,
It can be widely applied to the technical fields such as photoelectric device, energy storage device, safeguard function coating, catalysis material, composite material.
The invention has the advantages and beneficial effects that:
(1) roller fitting matrix of the present invention can be convenient taking-up film, can select corresponding base according to the wellability of liquid
Body material can also avoid film from needing transfer process in device fabrication process directly by device body as film forming matrix.
(2) present invention is rotated in the matrix surface being fitted on barrel by roller and generates uniformly adjustable centrifugal force field,
Sprawl the liquid for injecting matrix surface uniformly along surface, centrifugal force can be regulated and controled by controlling rotation speed and rotating cylinder radius
Field intensity makes force intensity be suitable for the liquid of different viscosities.
(3) present invention injects liquid by ink-jet mode, with accuracy controlling liquid injection zone and can inject flow, thus
Film is controlled in the film-forming region of matrix surface.
(4) curing process is passed through using the present invention, liquid film can be made to solidify under uniform effect of centrifugal force, to obtain
The film of uniform thickness, prepared uniform single film layer thickness can control 10nm or less.
(5) present invention prepare film process film it is high-efficient, complete the one-pass film-forming operating process shortest time only need 1
Second.
(6) present invention prepares film process and can prepare thickness using being layering repeatedly to reach grade even thicker
Single composition or multicomponent stacked in multi-layers composite membrane.
Detailed description of the invention
Fig. 1 (a)-(b) is the typical technical solution schematic diagram for being centrifuged ink-jetting process and preparing adjustable large area uniform film.Its
In, Fig. 1 (a) is perspective view, and Fig. 1 (b) is cross-sectional view；In figure, 1 rotating electric machine, 2 rotating cylinders, 3 optical wave heating pipes, the shifting of 4 syringe needles
Dynamic device, 5 film forming matrixes, 6 syringe needles.
Fig. 2 is the nano-level thin-membrane for the nanometer grade thickness that aqueous polyurethane is raw material preparation.Wherein, a aqueous polyurethane sprays
Matrix surface photo after the completion of ink, b waterborne polyurethane film step curve.
Fig. 3 is the nano-level thin-membrane for the nanometer grade thickness that aqueous polyurethane is raw material preparation.Wherein, a silver nanowires solution
Matrix surface photo after the completion of ink-jet, b silver nanowires film front SEM photograph.
Fig. 4 is the high starch breeding alkene film prepared using intrinsic graphene as raw material.Wherein, the highly directional film of a graphene is being just
Face material object photo, b, c are respectively the highly directional film cross-sectional scans electromicroscopic photograph of different-thickness graphene.
Specific embodiment
As shown in Fig. 1 (a)-(b), the rotating centrifugal that the present invention uses sprays membrane equipment, including rotating electric machine 1, rotation
Roller 2, optical wave heating pipe 3, syringe needle mobile device 4, film forming matrix 5, syringe needle 6 etc., specific structure is as follows:
For rotating electric machine 1 by the rotation horizontally disposed rotating cylinder 2 of axis connection, 3 level of optical wave heating pipe extends to rotation rolling
In cylinder 2, the syringe needle 6 of 4 one end of syringe needle mobile device is corresponding with 5 inner surface of film forming matrix of 2 inside of rotating cylinder, and form a film matrix
5 can rotate with rotating cylinder 2, and syringe needle mobile device 4 drives syringe needle 6 along the direction with 2 rotation axis horizontal of rotating cylinder with one
Determine speed translation, the injection film forming of syringe needle 65 surface of matrix that film forming liquid passes through syringe needle mobile device 4.
In the specific implementation process, the present invention can accuracy controlling nanometer grade thickness forming thin film thickness and area film side
Method is as follows:
(1) using rotating cylinder component described in Fig. 1 (a)-(b) rotating centrifugal spraying membrane equipment, make used in film forming
Film forming matrix, which is in, stablizes rotation status.Its specific operation process includes:
I. the film forming basis material suitable according to application demand selection, the film forming matrix are organic or inorganic film flexible
Material or sheet material, including but not limited to various resin films, such as: PET, PP, PC, PE；Resin compounded film, such as: being led with flexible ITO
The PET film etc. of electric layer；Metal film, such as: aluminium foil, copper foil, goldleaf, non-metallic film；Such as: soft graphite film, asbestos fibre film, soft
Property sheet glass etc..
II. the matrix to form a film will be needed to be tightly attached to rotating cylinder inner wall, patch matrix mode can be used but is not limited only to straight
It connects patch matrix plus sticker matrix and liquid feeding shows consideration for matrix.Matrix is directly pasted, i.e., is directly fitted in matrix curling in rotating cylinder
On wall；Add bond paper facing, i.e., glue is added between matrix and rotating cylinder inner wall and is bonded；Liquid feeding shows consideration for matrix, i.e., in matrix
Liquid is added between rotating cylinder inner wall, is bonded matrix and rotating cylinder inner wall using the capillarity of liquid.
III. film forming matrix rotation, the centrifugation for obtaining film forming substrate surface position because of rotation are driven by mechanical device
Acceleration is in the range of 0.1g~500000g, and the centrifugal acceleration range of optimization is that (wherein, g is gravity to 10g~10000g
Acceleration, numerical value 9.8m/s2), and keep stable.
It (2) will be certain in the case where constant film forming liquid pressure using printing head or syringe needle with micro-aperture
The film forming liquid of the film forming matter preparation of amount is ejected into the film forming matrix table being rotating with given pace in the form of fine fluid column
Face allows film forming liquid to be elongated to uniform fillet under shearing force and the collective effect of centrifugal force cyclic annular.Wherein, spray head
Or the pore diameter range of syringe needle is 1 μm~10cm, the pore diameter range of optimization is 10 μm~2mm；The range of film forming liquid pressure is
10Pa~100MPa, the pressure limit of optimization are 50kPa~5000kPa；Film forming matrix adds because of the centrifugation that centrifugal rotary transfers to obtain
Velocity interval be 0.1g~500000g, the centrifugal acceleration range of optimization be 10g~10000g (wherein g is acceleration of gravity,
Numerical value is 9.8m/s2)。
(3) film forming matter includes various high-molecular organic materials, two-dimensional material, one-dimensional material and zero dimension material etc..Wherein,
Organic polymer film includes but is not limited to polyimides (PI), polyurethane (PU), polyethylene (PE), epoxy resin, natural rubber
Glue, conducting high polymers object (poly- (3,4- ethene dioxythiophene)-polystyrolsulfon acid PEDOT:PSS), silicon rubber etc.；Two dimension
Material includes but is not limited to graphene, boron nitride, Transition-metal dichalcogenide (TMD), two-dimentional transition metal carbon or nitride
(MXenes), black phosphorus etc.；One-dimensional material includes carbon nanotube, silver nanowires, copper nano-wire, nanofiber etc.；Zero dimension material packet
Include but be not limited to nano silicon particles, nano SiO 2 particle, Titanium dioxide nanoparticle, carbon black, fullerene etc..
(4) film forming matter needs to be configured to the fluid states such as solution or suspension, in order to spray or inject.Solvent for use
Including various inorganic or organic solvent, and it may participate in the reactive organic diluents etc. of film forming.Wherein, inorganic solvent includes but not
It is limited to water, ionic liquid, acetic acid, sulfuric acid, liquefied ammonia etc.；Organic solvent include but is not limited to ethyl alcohol, propyl alcohol, acetone, benzene, chlorobenzene,
Toluene, dimethylbenzene, acetonitrile, ether and chloroform etc.；Reactive diluent includes but is not limited to alkylidene glycidol ether, neodecanoic acid contracting
Water glycerolipid, butyl glycidyl ether, toluene glycidol ether, castor oil polyglycidyl ether, hydroxyethyl methacrylate and
Hexanediyl ester etc..
(5) it in order to obtain the film-forming region of different in width, can be utilized while spray head or syringe needle injection film forming liquid
The mechanical device of process control translates spray head or syringe needle feed inlet with certain speed along the direction with roller rotation axis horizontal；
Spray head or the distance of syringe needle translation can be used to the width of regulation film-forming region, need can control spray head or needle according to film
Head repeatedly moves back and forth between the both ends of translation distance, and spray head or syringe needle need to be always in stable injection shapes in translation motion
State.By aforesaid operations, the continuous liquid film of setting width, the thickness model of liquid film can be formed in the film forming matrix surface of rotation
It encloses for 50nm~5000 μm, the thickness of liquid film of optimization is 500nm~500 μm.The above process is defined as a fluid injection operation stream
Journey.
(6) it needs to carry out curing process, curing process mistake to liquid film while completing a fluid injection operating process or later
Cheng Zhongxu keeps the rotation status of film forming matrix constant, that is, saves film forming matrix and be in stable centrifugal force field；Curing process side
Method include but is not limited to one of heating, drying, reduction vaporization, photocuring, heat cure, injection curing modes such as curing agent or
Two or more combinations.One-pass film-forming operation, one-pass film-forming operation gained film material are completed after the liquid film is fully cured
The thickness range of material is 1nm~500 μm, and the film forming thickness range of optimization is 5nm~5000nm, at film surface roughness
Range is 1nm~20nm.
(7) after completing one-pass film-forming operation, it can be required according to film or device manufacture requires, once or twice the above weight
Multiple above-mentioned Film forming operations process is changed to the film liquid of other materials or changes parameters of preparation, above once or twice to execute
Above-mentioned Film forming operations process, to obtain the thin-film material or two layers or more THIN COMPOSITE membrane material being constituted of heterogeneity of different-thickness
Material.
(8) after completing above-mentioned film operation, according to resulting devices or application requirement, gained thin-film material can be with film forming base
Body is used in conjunction with or removes simultaneously independent utility from film forming matrix surface in the case where film itself mechanical property allows.
Drawings and examples described in this specification are described in further detail to a specific embodiment of the invention, below
Three embodiments be but to be not intended to limit the scope of the invention for explanation of the invention.
Embodiment 1
As shown in Figure 2 a, in the present embodiment used film forming basis material be processed 125 μ m thick of surface hydrophilic PET
Film, using 150mm internal diameter, 100mm length aluminium alloy cylinder as rotating cylinder, PET is fitted into aluminium alloy rolling with ethyl alcohol
Cylinder inner wall, it is that (g is acceleration of gravity, numerical value 9.8m/s to 380g that PET matrix surface, which applies centrifugal acceleration,2).Injection nozzle
Using stainless steel syringe needle, 200 μm of syringe needle internal orifice dimension, needle length 50mm.Filmogen is aqueous polyurethane (WTPU), and solvent is
Water, aqueous polyurethane concentration are 1mg/ml.Syringe needle silica gel piping connection liquid pump, syringe needle, which is fixed on, to be automatically moved by program
Bracket on.Aqueous polyurethane aqueous solution feeding syringe needle is injected into the pet sheet face of rotation by liquid pump, and liquid pump applies pressure and is
0.3MPa, syringe needle is uniformly moved along axial rotary direction in injection liquid process, and control moving distance is 8cm, liquid edge
Pet sheet face formation width be 8cm liquid film.Then water is vapored away using the liquid film in optical wave heating pet sheet face form film, institute
The polyurethane transparent film light transmittance of preparation is close to 100%, with a thickness of 100nm.
As shown in Figure 2 b, it is only from the thickness that waterborne polyurethane film step curve can be seen that the thin polymer film
100nm, surface roughness are less than 20nm, and it is suitable which with physical vapour deposition (PVD) (PVD) prepares the effect of film.
Embodiment 2
As shown in Figure 3a, in the present embodiment used film forming basis material be 188 μ m-thicks PET film, using 150mm, interior
For the aluminium alloy cylinder of diameter 100mm length as rotating cylinder, PET matrix is placed directly against aluminium alloy inner wall of rotary drum, and PET matrix surface is applied
Adding centrifugal acceleration is that (g is acceleration of gravity, numerical value 9.8m/s to 500g2), injection nozzle uses stainless steel syringe needle, in syringe needle
300 μm, needle length 50mm of aperture, using silver nanowires as film forming raw material, solvent is dehydrated alcohol, and silver nanowires concentration is
2mg/ml, syringe needle silica gel piping connection liquid pump, syringe needle is fixed on can be by the bracket that program automatically moves.Liquid pump will be silver-colored
Nanowire dispersion is sent into the PET film surface that syringe needle is injected into rotation, and it is 0.2MPa that liquid pump, which applies pressure, in injection liquid mistake
Syringe needle is uniformly moved along axial rotary direction in journey, and control moving distance is 8cm, and liquid is along PET film surface formation width
For the liquid film of 8cm.Then the silver nanowires film that ethyl alcohol forms nanometer grade thickness is vapored away using optical wave heating liquid film, it is prepared
Silver nanowires sheet resistance is 8 Ω/, light transmittance 86%.
As shown in Figure 3b, from silver nanowires film front, SEM photograph can be seen that the silver nanoparticle for constituting transparent conductive film
Line is evenly distributed in the threadiness stretched, soilless sticking phenomenon, and has certain directionality, and this structure guarantees transparent conductive film
Excellent properties.
Embodiment 3
As shown in fig. 4 a, used film forming basis material is fluorination release film in the present embodiment, using 350mm internal diameter, 250mm
The aluminium alloy cylinder of length fits to aluminium alloy inner wall of rotary drum for release film is fluorinated as rotating cylinder, with ethyl alcohol, is fluorinated release film
It is that (g is acceleration of gravity, numerical value 9.8m/s to 400g that matrix surface, which applies centrifugal acceleration,2).Injection nozzle uses polytetrafluoro
Ethylene material syringe needle, 350 μm of syringe needle internal orifice dimension, needle length 100mm.Using intrinsic graphene as film forming raw material, water conduct
Solvent, intrinsic graphene concentration are 2.5mg/ml.Syringe needle connects liquid pump with polytetrafluoroethylene (PTFE) pipeline, and liquid pump is by intrinsic graphite
Alkene dispersion liquid is sent into the fluorination release film matrix surface that syringe needle is injected into rotation, and it is 0.15MPa that liquid pump, which applies pressure, is injecting
Syringe needle is uniformly moved along axial rotary direction in liquid process, and control moving distance is 18cm, then utilizes optical wave heating liquid
Film vapors away water and forms the first layer film, as the operation of completion one-pass film-forming.Using identical intrinsic graphene dispersing solution, repeatedly
Above-mentioned Film forming operations process is executed, by controlling the Film forming operations number of plies, the thin-film material of different-thickness is can be obtained, then again will
Film forms self-supporting independent film from removing on fluorination release film matrix, Fig. 4 b and Fig. 4 c show respectively with a thickness of 16 μm and
75 μm of intrinsic graphene film, resulting intrinsic graphene film have highly directional layer structure, and area reaches 1800cm2,
Its film conductivity reaches 1300S/cm, and mechanical stretch intensity is 150MPa.
Three above embodiment realizes the film preparation of organic material, one-dimensional material, two-dimensional material, thickness it is controllable from
100nm to 75 μm, the film preparation of compatible organic material and nano material.The limitation for overcoming traditional film-forming method, for receiving
The film of rice material and organic material assembling preparation and laminated film preparation provide efficient solution.
It is three kinds of preferred embodiments of the invention above, is not intended to restrict the invention.Wherein prepare each of film
Link can also do several improvement, in the improvement for the principle for not departing from this technology of the present invention, also should be regarded as protection model of the invention
It encloses.
Claims (8)
1. one kind can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method, which is characterized in that including such as
Lower step:
(1) membrane equipment is sprayed using rotating centrifugal, is in film forming used film forming matrix and stablizes rotation status；
(2) spray head with hole or syringe needle are used, in the case where constant film forming liquid pressure, by the film forming of film forming matter preparation
Liquid is ejected into the film forming matrix surface being rotating in the form of fluid column, makes film forming liquid in the common work of shearing force and centrifugal force
It is cyclic annular that uniform fillet is elongated under；
(3) in order to which the film-forming region for obtaining different in width utilizes process control while spray head or syringe needle injection film forming liquid
Mechanical device make spray head or syringe needle feed inlet along with the translation of the direction of roller rotation axis horizontal；Spray head or syringe needle translation away from
From being width for regulating and controlling film-forming region, according to film to need to control spray head or syringe needle past between the both ends of translation distance
Multiple movement, spray head or syringe needle are in stable injection state always in translation motion；By aforesaid operations, in the film forming base of rotation
Body surface face, forms the continuous liquid film of setting width, and the above process is defined as a fluid injection operating process；
(4) curing process is carried out to liquid film while completing a fluid injection operating process or later, is protected during curing process
The rotation status for holding film forming matrix is constant, that is, saves film forming matrix and be in stable centrifugal force field, be fully cured in the liquid film
One-pass film-forming operation is completed afterwards；
(5) after completing one-pass film-forming operation, required according to film or device manufacture require, it is above once or twice repeat it is above-mentioned
Film forming operations process is changed to the film liquid of other materials or changes parameters of preparation, it is above once or twice execute it is above-mentioned at
Membrane operations process, to obtain the thin-film material or two layers or more composite film material being constituted of heterogeneity of different-thickness；
(6) after completing above-mentioned film operation, according to resulting devices or application requirement, gained thin-film material makes jointly with film forming matrix
In the case where permission with or film itself mechanical property, from the removing of film forming matrix surface and independent utility.
2. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It is characterized in that, in step (1), it includes: rotating electric machine, rotating cylinder, optical wave heating pipe, syringe needle that rotating centrifugal, which sprays membrane equipment,
Mobile device, film forming matrix, syringe needle, specific structure are as follows:
Rotating electric machine is extended in rotating cylinder by the rotation horizontally disposed rotating cylinder of axis connection, optical wave heating pipe level, needle
The syringe needle of head moving device one end is corresponding with the film forming base inner surface on the inside of rotating cylinder, and film forming matrix is revolved with rotating cylinder
Turn, syringe needle mobile device drives syringe needle to translate along with the direction of rotary drum rotating axis level, and film forming liquid passes through syringe needle and moves
The syringe needle injection film forming matrix surface of dynamic device.
3. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It is characterized in that, in step (1), the specific operation process of rotating centrifugal spraying film includes:
I. according to application demand select film forming basis material, the film forming matrix be organic or inorganic membrane material flexible or sheet material,
Including but not limited to various resin films, resin compounded film, metal film or non-metallic film；
II. the matrix that forms a film will be needed to be tightly attached to rotating cylinder inner wall, patch matrix mode use but be not limited only to directly paste matrix,
Sticker matrix or liquid feeding is added to show consideration for matrix；Matrix is directly pasted, i.e., is directly fitted in matrix curling on rotating cylinder inner wall；Add glue
Pad pasting is added glue that is, between matrix and rotating cylinder inner wall and is bonded；Liquid feeding shows consideration for matrix, i.e., in matrix and rotating cylinder
Liquid is added between inner wall, is bonded matrix and rotating cylinder inner wall using the capillarity of liquid；
III. film forming matrix rotation, the CENTRIFUGAL ACCELERATING for obtaining film forming substrate surface position because of rotation are driven by mechanical device
Degree is in the range of 0.1g~500000g, and g is acceleration of gravity, numerical value 9.8m/s2, and keep stable.
4. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
Be characterized in that, in step (2), the pore diameter range of spray head or syringe needle is 1 μm~10cm, the range of film forming liquid pressure be 10Pa~
100MPa, it is 0.1g~500000g that film forming matrix, which transfers the centrifugal acceleration range obtained because of centrifugal rotary, and g is acceleration of gravity,
Numerical value is 9.8m/s2。
5. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It is characterized in that, film forming matter includes various high-molecular organic materials, two-dimensional material, one-dimensional material or zero dimension material；Wherein, organic
Macromolecule membrane includes but is not limited to polyimides, polyurethane, polyethylene, epoxy resin, natural rubber, PEDOT:PSS or silicon
Rubber；Two-dimensional material include but is not limited to graphene, boron nitride, Transition-metal dichalcogenide, two-dimentional transition metal carbide,
Two-dimentional transition metal nitride or black phosphorus；One-dimensional material includes carbon nanotube, silver nanowires, copper nano-wire or nanofiber；Zero
Tieing up material includes but is not limited to nano silicon particles, nano SiO 2 particle, Titanium dioxide nanoparticle, carbon black or fullerene.
6. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It being characterized in that, film forming matter is configured to solution or suspension fluid state, and solvent for use includes various inorganic or organic solvent, or
Person may participate in the reactive organic diluents of film forming；Wherein, inorganic solvent include but is not limited to water, ionic liquid, acetic acid, sulfuric acid or
Liquefied ammonia；Organic solvent includes but is not limited to ethyl alcohol, propyl alcohol, acetone, benzene, chlorine benzene,toluene,xylene, acetonitrile, ether or chloroform；
Reactive diluent includes but is not limited to alkylidene glycidol ether, neodecanoic acid glycidol rouge, butyl glycidyl ether, toluene contracting
Water glycerin ether, castor oil polyglycidyl ether, hydroxyethyl methacrylate or hexanediyl ester.
7. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It is characterized in that, in step (3), the thickness range of liquid film is 50nm~5000 μm.
8. it is described in accordance with the claim 1 can accuracy controlling nanometer grade thickness forming thin film thickness and area film-forming method,
It is characterized in that, in step (4), solidification processing method includes but is not limited to heating, drying, reduction vaporization, photocuring, heat cure, note
Enter the combination of one or more of curing agent curing mode；One-pass film-forming operation gained thin-film material thickness range be
1nm~500 μm, at film range of surface roughness be 1nm~20nm.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040222A (en) * | 2019-12-19 | 2020-04-21 | 中国科学院金属研究所 | Preparation method of graphene electromagnetic shielding film |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669668A (en) * | 2005-04-08 | 2005-09-21 | 华南理工大学 | Synchronous load quick film-forming method for nano functional film |
| CN202061773U (en) * | 2010-07-23 | 2011-12-07 | 向熙科技股份有限公司 | Spin-coating device |
| CN203270016U (en) * | 2013-05-03 | 2013-11-06 | 中化二建集团有限公司 | Thermal spraying device for carbon steel metal surface |
| CN108906377A (en) * | 2018-09-10 | 2018-11-30 | 南京膜材料产业技术研究院有限公司 | A kind of spraying equipment of multi-level asymmetric ceramic-film tube |
| CN109177010A (en) * | 2018-10-10 | 2019-01-11 | 深圳烯材科技有限公司 | A kind of rotary spraying membrane equipment |
-
2019
- 2019-05-30 CN CN201910460855.5A patent/CN110274803A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669668A (en) * | 2005-04-08 | 2005-09-21 | 华南理工大学 | Synchronous load quick film-forming method for nano functional film |
| CN202061773U (en) * | 2010-07-23 | 2011-12-07 | 向熙科技股份有限公司 | Spin-coating device |
| CN203270016U (en) * | 2013-05-03 | 2013-11-06 | 中化二建集团有限公司 | Thermal spraying device for carbon steel metal surface |
| CN108906377A (en) * | 2018-09-10 | 2018-11-30 | 南京膜材料产业技术研究院有限公司 | A kind of spraying equipment of multi-level asymmetric ceramic-film tube |
| CN109177010A (en) * | 2018-10-10 | 2019-01-11 | 深圳烯材科技有限公司 | A kind of rotary spraying membrane equipment |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040222A (en) * | 2019-12-19 | 2020-04-21 | 中国科学院金属研究所 | Preparation method of graphene electromagnetic shielding film |
| CN111718572A (en) * | 2020-06-18 | 2020-09-29 | 工科思维技术(深圳)有限公司 | Preparation method of two-dimensional nano polymer composite wire suitable for 3D printing |
| CN114057184A (en) * | 2020-07-31 | 2022-02-18 | 北京大学 | Density regulating method and preparation device of self-supporting carbon nanotube film target |
| CN114057184B (en) * | 2020-07-31 | 2023-06-09 | 北京大学 | Density regulation and control method and preparation device of self-supporting carbon nanotube film target |
| CN112341848A (en) * | 2020-11-05 | 2021-02-09 | 上海理工大学 | Graphene coating and preparation method of graphene conductive corrosion-resistant coating |
| CN112456480A (en) * | 2020-12-02 | 2021-03-09 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | Graphene membrane material, preparation method and application thereof |
| CN112456480B (en) * | 2020-12-02 | 2023-10-27 | 江西省纳米技术研究院 | Graphene membrane material, preparation method and application thereof |
| CN113555162A (en) * | 2021-07-13 | 2021-10-26 | 郑州大学 | Preparation method of highly-oriented one-dimensional conductive filler-based TCF (thermal conductive film) material |
| CN113555162B (en) * | 2021-07-13 | 2022-07-22 | 郑州大学 | Preparation method of highly-oriented one-dimensional conductive filler-based TCF (thermal conductive film) material |
| CN113441305A (en) * | 2021-07-13 | 2021-09-28 | 郑州大学 | One-dimensional conductive filler spraying device for TCF preparation |
| CN115157511A (en) * | 2022-06-19 | 2022-10-11 | 北京工业大学 | Device capable of regulating and controlling thickness and uniformity of high-viscosity fluid film |
| CN115157511B (en) * | 2022-06-19 | 2023-09-12 | 北京工业大学 | Device capable of regulating and controlling film forming thickness and uniformity of high-viscosity fluid |
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