CN110240117A - Ultrathin transparent nano/micron structure self-assembled film and its environment-friendly preparation method thereof - Google Patents
Ultrathin transparent nano/micron structure self-assembled film and its environment-friendly preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B1/00—Devices without movable or flexible elements, e.g. microcapillary devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00214—Processes for the simultaneaous manufacturing of a network or an array of similar microstructural devices
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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
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention discloses a kind of ultrathin transparent nano/micron structure self-assembled film and its environment-friendly preparation method thereofs.The preparation method includes: to disperse formation nano/micron structure dispersion liquid in the first liquid-phase system for nano/micron structure and/or its modifier；Nano/micron structure dispersion liquid is sprayed to second liquid phase system surface with spray pattern, then removes the second liquid phase system, obtains nano/micron structure film；Extrusion process is carried out to the nano/micron structure film, the nano/micron structure film is made to carry out self assembly on gas-liquid interface and form the controllable nano/micron structure self-assembled film of form compact and stable thickness.Nano/micrometre particle and its modifier film comprehensive performance of the invention can well be widely used in optics, electricity device, on nano coating；Preparation process flow of the present invention is simple and convenient to operate, is low to environmental factor requirement simultaneously, and does not have any impact, and meets industrial large area, production demand.
Description
Technical field
The present invention relates to a kind of environment-friendly preparation method thereofs of nano/micron structure self-assembled film, in particular to one kind can be certainly
The ultrathin transparent of support is conductive, the self-assembled film including multi-dimension nano/micro particles or line and its environment-friendly preparation method thereof and
Using belonging to material science and technology field.
Background technique
Self-assembled nanometer film is that have the molecule of certain function characteristic by chemical bond, Spontaneous adsorption solid one
One liquid/solid interface of liquid, one liquid of gas or gas, the lower order thin film of Thermodynamically stable and energy of formation are mainly characterized by original position certainly
Formation, Thermodynamically stable, molecular ordered arrangement, high density accumulation and low defect density are sent out, it can be by artificially designing molecule knot
Structure and surface texture obtain expected surface physics and chemical property.Self-assembled film technology of preparing mainly includes electrostatic force from group
Dress, covalent bond self-assembly and molecule deposition self assembly etc..
Wherein, two aspect of basic theory and practical application is covered in air-to-water interface nano thin-film self assembly research, is related to
Biological medicine, life science such as cell membrane, paint, the food such as cooling rear surface conjunctiva of the dense milk of heat, hot dense soy milk, petroleum
Exploitation and processing, the daily-use chemical industry such as numerous areas such as detergent, cosmetics and new material.Air-to-water interface nano thin-film
In preparation preparation transparent conductive film, super-hydrophobic figure layer, nanometer or micro ordered array, nanoparticle or nano wire self assembly, receive
The preparation of rice catalyst preparation, the preparation of Raman reinforcing material, new catalytic material and photoelectric material etc. provides new approach.
In recent years, people have developed a variety of methods for preparing continuous nano/micrometre particle and its modifier film.At present
Usually there is preparation method complex process, equipment requirement height, need to make in the method for preparing nano/micrometre particle and its modifier film
With toxic solvent, be not suitable for large-scale production the defects of.Therefore, simple and environmentally-friendly, efficient prepare how is developed continuously to surpass
Thin nano/micrometre particle self-assembled film is one of the significant challenge that field scientific worker faces.
Summary of the invention
In view of the deficiencies in the prior art, the main purpose of the present invention is to provide it is a kind of can self-supporting ultrathin transparent it is conductive
Nano/micron structure self-assembled film and its environment-friendly preparation method thereof and application.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of the green of ultrathin transparent nano/micron structure self-assembled film is provided among some embodiments of the invention
Color preparation method comprising:
(1) it disperses the modifier of nano/micron structure and/or nano/micron structure in the first liquid-phase system and is formed
Nano/micron structure dispersion liquid；
(2) nano/micron structure dispersion liquid is sprayed to by second liquid phase system surface with spray pattern, to the first liquid phase body
After system's volatilization, then the second liquid phase system is removed, obtains nano/micron structure film；
(3) extrusion process is carried out to the nano/micron structure film using surface tension of liquid, makes the nanometer/micro-
Rice structural membrane carries out self assembly on gas-liquid interface and forms form compact and stable nano/micron structure film, and it is equal to obtain structure
Even controllable nano/micron structure self-assembled film；
Wherein, point of the modifier of the nano/micron structure and/or nano/micron structure in the first liquid-phase system
Divergence is greater than the dispersion degree in second liquid phase system, and the first liquid-phase system cannot dissolve each other with second liquid phase system.
In some embodiments, the preparation method includes: that nano/micron structure dispersion liquid is sprayed to second liquid phase body
When being surface, the spray velocity used is 5ml/min~500ml/min.
In some embodiments, the preparation method includes: using peristaltic pump pumps mode by the second liquid phase system
It removes.
Further, use the rate of second liquid phase system described in peristaltic pump pumps for 5mL/min~20mL/min.
Preferably, the time of the extrusion process is 5s~60s.
Preferably, the pressure that the extrusion process uses is 7.2~7.8mN/m.
In some embodiments, the preparation method further includes step (4): by the ultrathin transparent nano/micron structure
Self-assembled film is transferred to selected interface and is self-assembly of by the mixed film of different structure nano film LBL self-assemblies.
Preferably, the mixed film includes the modifier of at least one nano/micron structure or nano/micron structure.
Further, the preparation method further include: circulating repetition carries out step (3) and/or step (4) more than twice,
Until the ultrathin transparent nano/micron structure self-assembled film needed for obtaining.
Further, cycle-index is 5~10 times.
Further, the modifier of the nano/micron structure and/or nano/micron structure includes one-dimensional material, two dimension
Material or three-dimensional material.
Further, the nano/micron structure and/or the modifier of nano/micron structure at least one dimension
Size is greater than 1 nanometer and less than 1000 microns.
Further, the nano/micron structure includes nano/micrometre particle and/or Nano/micron line.
Further, the nano/micrometre particle include metal nanoparticle, metal and/or nonmetal oxide particle,
Any one in polymer particle and nano-carbon material or two or more combinations.
Further, self assembly temperature of the nano/micron structure film on gas-liquid interface is 20~100 DEG C, when
Between be 10s~1000s.
The ultrathin transparent nano/micron structure prepared by preceding method is additionally provided among some embodiments of the invention
Self-assembled film.
Preferably, the film with a thickness of 20nm~10 μm, surface roughness is less than 1.5nm, and light transmittance is greater than 86%.
Additionally provided among some embodiments of the invention aforementioned ultrathin transparent nano/micron structure self-assembled film in
Prepare transparent devices, transparent conductive film, super-hydrophobic coat, nanometer or micro ordered array, nanoparticle or nano wire self assembly
Purposes in material, nano-catalyst material or Raman reinforcing material.
For example, it includes ultrathin transparent nano/micron structures above-mentioned certainly the embodiment of the invention also provides a kind of device
Component film.
Preferably, described device includes Optical devices, electronic device or photoelectron device.
Compared with prior art, beneficial effects of the present invention at least that:
1) the environment-friendly preparation method thereof simple process of ultrathin transparent nano/micron structure self-assembled film provided by the invention,
Easy to implement, without expensive apparatus for preparation, high temperature action and catalyst, time-consuming is few；
2) environment-friendly preparation method thereof of ultrathin transparent nano/micron structure self-assembled film provided by the invention is received by control
The thickness of nano/micrometre particle and its modifier film can be effectively controlled in the concentration of rice/micro particles and its modifier dispersion liquid；
3) only make in the environment-friendly preparation method thereof cleaning of ultrathin transparent nano/micron structure self-assembled film provided by the invention
With second alcohol and water, the surface contamination of nano/micrometre particle and its modifier film can be reduced, while environmental-friendly, it is simple and environmentally-friendly；
4) nano/micrometre particle and its modifier conductive film that the present invention is prepared have good intensity, can shape
At stable self supporting structure；
5) nano/micrometre particle that is prepared of the present invention and its modifier conductive film electric conductivity is good, transparency
It is higher, it can be applied on transparent or conductive devices.
In short, nano/micrometre particle prepared by the present invention and its modifier film comprehensive performance can be well widely used in
On light, electrical part.Preparation method process flow of the invention simultaneously is simple and convenient to operate, is low to environmental factor requirement, and does not make
At any influence, meet industrial large area, production demand, effect is obvious, can continuously collect Nano/micron grain on a large scale
Son and its modifier film.
Detailed description of the invention
Fig. 1-Fig. 2 is the process that ultrathin transparent polystyrene microsphere self-assembled film is prepared in the embodiment of the present invention 1 respectively
Schematic diagram.
Fig. 3 is the photo figure in kind of obtained ultrathin transparent polystyrene microsphere self-assembled film in the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscopy of obtained ultrathin transparent polystyrene microsphere self-assembled film in the embodiment of the present invention 1
Mirror.
Specific embodiment
More detailed explanation will hereafter be made to technical solution of the present invention.It is understood, however, that in model of the present invention
In enclosing, above-mentioned each technical characteristic of the invention and it is ok between each technical characteristic specifically described in below (e.g. embodiment)
It is combined with each other, to form a new or preferred technical solution.Due to space limitations, I will not repeat them here.
As previously mentioned, in view of many deficiencies of the prior art, inventor's in-depth study and a large amount of by long-term
Practice is able to propose technical solution of the present invention, is mainly based upon particle (or line) of the size at several nanometers to several hundred microns
These particle/lines are made to be self-assembled into a kind of environment-friendly preparation method thereof of ultrathin film at gas-liquid interface by simple spray-on process.
For example, it is sprayed onto liquid level by sprayer using the dispersion liquid of nano/micrometre particle and its modifier, then by squeezing table
The particle in face forms fine and close ultrathin membrane.The technical solution, its implementation process and principle etc. will be made as follows into one in conjunction with attached drawing
The explanation of step.
The present invention provides a kind of preparation method of ultrathin transparent nano/micron structure self-assembled film, the thickness of film
Degree, transparency, electric conductivity can pass through the amount and nano/micron structure and/or its modification of penetrating nano/micron structure dispersion liquid
The concentration of object is adjusted.
The one aspect of the embodiment of the present invention provides a kind of green of ultrathin transparent nano/micron structure self-assembled film
Preparation method comprising:
(1) by nano/micron structure (composite construction that should be understood nanostructure, micrometer structure or both) and/or
The modifier of nano/micron structure is scattered in formation nano/micron structure dispersion liquid in the first liquid-phase system；
(2) nano/micron structure dispersion liquid is sprayed to by second liquid phase system surface with spray pattern, to the first liquid phase body
After system's volatilization, then the second liquid phase system is removed, obtains nano/micron structure film；
(3) extrusion process is carried out to the nano/micron structure film using surface tension of liquid, makes the nanometer/micro-
Rice structural membrane carries out self assembly on gas-liquid interface and forms form compact and stable nano/micron structure film, and it is equal to obtain structure
Even controllable nano/micron structure self-assembled film；
Wherein, point of the modifier of the nano/micron structure and/or nano/micron structure in the first liquid-phase system
Divergence is greater than the dispersion degree in second liquid phase system, and the first liquid-phase system cannot dissolve each other with second liquid phase system.
Wherein, first liquid-phase system is preferably effumability liquid-phase system.
Wherein, the modifier of the nano/micron structure and/or nano/micron structure is one-dimensional, two-dimentional or three-dimensional material
Material.
In some embodiments, the preparation method includes: that nano/micron structure dispersion liquid is sprayed to second liquid phase body
When being surface, the spray velocity used is 5ml/min~500ml/min.
Further, when nano/micron structure dispersion liquid being sprayed to second liquid phase system surface, what spray head generated is sprayed
Area and the film forming area (the aimed thin film area prepared) of the nano/micron structure film of preparation are identical or close.
Further, in spray process, the size of the drop of sprinkling is 5*10-3Mm~5*10-1mm。
In some embodiments, the preparation method includes: using peristaltic pump pumps mode by the second liquid phase system
It removes.
Further, use the rate of second liquid phase system described in peristaltic pump pumps for 5mL/min~20mL/min.
Preferably, the time of the extrusion process is 5s~60s.
Preferably, the pressure that the extrusion process uses is 7.2~7.8mN/m.
In some embodiments, the preparation method further includes step (4): by the ultrathin transparent nano/micron structure
Self-assembled film is transferred to other selected interface (solid phase interface or liquid interfaces) and is self-assembly of to be received by different structures
The mixed film of rice film LBL self-assembly.
Preferably, the mixed film includes the modifier of at least one nano/micron structure or nano/micron structure.
Further, the preparation method further include: circulating repetition carries out step (3) and/or step (4) more than twice,
Until the ultrathin transparent nano/micron structure self-assembled film needed for obtaining.
Further, cycle-index is 5~10 times.
In some embodiments, the preparation method further include: by nano/micron structure and/or nano/micron structure
Modifier is added in the first liquid-phase system, carries out ultrasonic disperse, forms nano/micron structure dispersion liquid.
Further, the time of the ultrasonic disperse is 0.5~20h.
Preferably, first liquid-phase system include any one or two kinds in ethyl alcohol, propyl alcohol, glycerine and water etc. with
On combination, but not limited to this, wherein needing to pay attention to component when combination and cannot dissolve each other with second liquid phase system.
Preferably, the concentration of the nano/micron structure dispersion liquid is 0.005mg/mL~2.0mg/mL.It is received by control
The thickness of nano/micrometre particle and its modifier film can be effectively controlled in the concentration of rice/micro particles and its modifier dispersion liquid.
In some embodiments, the modifier of the nano/micron structure is blended with modifying agent by nano/micron structure
Or graft reaction is formed.
Preferably, the modifier of the nano/micron structure includes organic matter and/or inorganic matter.
Preferably, the preparation method of the modifier of the nano/micron structure include: make comprising nano/micron structure and
The uniform hybrid reaction system of modifying agent is centrifuged in 40~60 DEG C of 4~7h of reaction, dry.
Preferably, the modifying agent includes oligomer and/or polymer biological macromolecular.
Further, the modified group that the modifier of the nano/micron structure includes includes-NH2,-COOH and-OH etc.
In any one or two or more combinations, but not limited to this.
Further, the modifier of the nano/micron structure and/or nano/micron structure includes one-dimensional material, two dimension
Material or three-dimensional material.
Further, the nano/micron structure and/or the modifier of nano/micron structure at least one dimension
Size is less than 1000 microns (at several nanometers between several hundred microns) greater than 1 nanometer.
Further, the nano/micron structure include nano/micrometre particle (nanoparticle, micro particles or both
Composite construction) and/or Nano/micron line (composite construction of nano wire, micro wire or both).
Further, the nano/micrometre particle includes metal nanoparticle, for example, nanogold or nano silver particles etc.；
It can also include metal and nonmetal oxide particle, for example, Nano particles of silicon dioxide, titanium dioxide nano-particle, four oxygen
Change three ferromagnetism nanometer particles etc.；It can also include polymer particle, for example, polystyrene microsphere and its modifier etc.；May be used also
To include nano-carbon material, for example, carbon nanotube, graphene, bucky-ball, carbon black pellet etc., but not limited to this.
In some embodiments, the second liquid phase system includes that water, carbon disulfide, chloroform, ionic liquid etc. are organic molten
Agent, wherein needing to pay attention to component when combination cannot dissolve each other with the first liquid-phase system.
Further, self assembly temperature of the nano/micron structure film on gas-liquid interface is 20~100 DEG C, when
Between be 10s~1000s.
Among one more specifically case study on implementation, the preparation method includes:
1) one or more nano/micrometre particles or its modifier are provided；
2) nano/micrometre particle is uniformly dispersed in certain solvent；
3) surface of solution is sprayed by spraying method dispersion liquid；
4) solution is extracted out to obtain nano/micrometre particle film by peristaltic pump or other instruments or material；
5) the nano/micrometre particle film is carried out being self-assembly of on gas-liquid interface fine and close and stable thin
Film；
6) formation film is transferred to other interface self assemblies and is further formed mixed film；
7) by circulation, to form the mixed film that multilayer is made of one or more nano/micrometre particles.
And among one more specifically embodiment, which can further include:
1, a certain amount of nano/micrometre particle and its modifier are taken, is added a certain amount of functional modification agent, 40~60 DEG C
Water-bath 4h~7h is centrifuged, dry.
2, the nano/micrometre particle of functionalization and its modifier are subjected to ultrasonic disperse with certain solvent, concentration is
0.05mg/mL~2mg/mL obtains nano/micrometre particle and its modifier dispersion liquid；
3, the resulting nano/micrometre particle of step 2 and its modifier dispersion liquid are sprayed onto certain solution by sprayer
Interface is then again extracted out solution with certain rate by peristaltic pump, nanometer uniform so as to form thickness, transparent/micro-
Rice corpuscles and its modifier film；
4, resulting uniform, the transparent nano/micrometre particle of step 3 and its modifier film are passed through into the objects such as peristaltic pump
The method for drawing interfacial liquid squeezes, and forms the nano/micrometre particle and its modifier film of uniform, transparent densification；
5, the resulting nano/micrometre particle of step 4 and its modifier hybrid film are further transferred to any solid circle
Face；
6, the resulting nano/micrometre particle of step 5 and its modifier hybrid film are stood, dry, repetitive operation step 4
With step 5, thus obtain it is a kind of can self-supporting ultrathin transparent electrical-conductive nanometer/micro particles and its modifier film.
It is only used in the environment-friendly preparation method thereof cleaning of ultrathin transparent nano/micron structure self-assembled film provided by the invention
Second alcohol and water can reduce the surface contamination of nano/micrometre particle and its modifier film, while environmental-friendly, simple and environmentally-friendly.
The environment-friendly preparation method thereof simple process of ultrathin transparent nano/micron structure self-assembled film provided by the invention, easily
In implementation, without expensive apparatus for preparation, high temperature action and catalyst, time-consuming is few.
The other side of the embodiment of the present invention additionally provides the ultrathin transparent nano/micron structure prepared by preceding method
Self-assembled film.
Preferably, the film with a thickness of 20nm~10 μm, surface roughness is less than 1.5nm, and light transmittance is greater than 86%,
Its result can be satisfied with the preparation of transparent devices etc..
Further, the film includes being made of the modifier of nano/micron structure and/or nano/micron structure
Nano/micron structure array and/or nano/micron structure network.
In some embodiments, the modifier of the nano/micron structure is blended with modifying agent by nano/micron structure
Or graft reaction is formed.
Preferably, the modifier of the nano/micron structure includes organic matter and/or inorganic matter.
Further, the nano/micron structure include nano/micrometre particle (nanoparticle, micro particles or both
Composite construction) and/or Nano/micron line (composite construction of nano wire, micro wire or both).
The other side of the embodiment of the present invention additionally provide aforementioned ultrathin transparent nano/micron structure self-assembled film in
Prepare transparent devices, transparent conductive film, super-hydrophobic coat, nanometer or micro ordered array, nanoparticle or nano wire self assembly
Material, nano-catalyst material or Raman reinforcing material etc. have potential application value.
For example, it includes ultrathin transparent nano/micron structures above-mentioned certainly the embodiment of the invention also provides a kind of device
Component film.
Preferably, described device includes Optical devices, electronic device or photoelectron device.
By above-mentioned technical proposal, the obtained nano/micrometre particle of the present invention and its modifier conductive film have well
Intensity can form stable self supporting structure；And electric conductivity is good, transparency is higher, can be applied to transparent or conductive devices
On.
In short, nano/micrometre particle prepared by the present invention and its modifier film comprehensive performance can be well widely used in
On light, electrical part.Preparation method process flow of the invention simultaneously is simple and convenient to operate, is low to environmental factor requirement, and does not make
At any influence, meet industrial large area, production demand, effect is obvious, can continuously collect Nano/micron grain on a large scale
Son and its modifier film.
Below in conjunction with several preferred embodiments the technical solution of the present invention is further explained explanation.
Embodiment 1
1, as depicted in figs. 1 and 2, a certain amount of polystyrene microsphere is taken to carry out ultrasonic disperse, concentration with certain ethyl alcohol
It is 2mg/mL；
2, the resulting polystyrene microsphere dispersion liquid of step 1 is sprayed onto water by sprayer with the spray velocity of 5ml/min
Interface, in spray process, the size of the drop of sprinkling is 5*10-3Mm, then again by peristaltic pump with the rate of 5ml/min
Solution is extracted out, is 20~60 DEG C of range self assembly 800s in temperature, is formed thin with a thickness of 5~10 μm of polystyrene microsphere
Film；
3, resulting uniform, the transparent polystyrene microsphere film of step 2 is drawn into interface liquid by objects such as peristaltic pumps
The method of body is with the pressure extrusion 60s of 7.2mN/m, the self assembly 800s at 40 DEG C, forms the polystyrene of uniform, transparent densification
Microballoon film；
4, the resulting polystyrene microsphere film of step 3 is further transferred to any solid interface；
5, the resulting polystyrene microsphere film of step 4 is stood, dry, repetitive operation step 4, so that obtaining one kind can
The uniform polystyrene microsphere film of the ultrathin of self-supporting, with a thickness of 10 μm, surface roughness is less than 1.5nm, light transmittance
Greater than 86%, appearance structure characterizes map referring to Fig. 3 and Fig. 4.
After tested, polystyrene microsphere film comprehensive performance manufactured in the present embodiment is good, can be widely used in light, electric appliance
On part.This method process flow simultaneously is simple and convenient to operate, is low to environmental factor requirement, and does not have any impact, and meets work
Sparetime university's area, production demand.
Embodiment 2
1, a certain amount of decorated by nano-gold polystyrene microsphere is taken to carry out ultrasonic disperse with certain ethyl alcohol, concentration is
0.05mg/mL；
2, the resulting decorated by nano-gold polystyrene microsphere dispersion liquid of step 1 is passed through into sprayer with the spray of 200ml/min
Mist speed is sprayed onto the interface of carbon disulfide, and in spray process, the size of the drop of sprinkling is 5*10-1Mm, then again by compacted
Dynamic pump is extracted out solution with the rate of 20mL/min, so as to form micro- with a thickness of 5~10 μm of decorated by nano-gold polystyrene
Ball film；
3, resulting uniform, the transparent decorated by nano-gold polystyrene microsphere film of step 2 is passed through into the objects such as peristaltic pump
The method of interfacial liquid is drawn with the pressure extrusion 5s of 7.8mN/m, the self assembly 1000s at 20 DEG C is formed conductive uniform, transparent
Fine and close decorated by nano-gold polystyrene microsphere film；
4, the resulting polystyrene microsphere film of step 3 is further transferred to any solid interface；
5, the resulting decorated by nano-gold polystyrene microsphere film of step 4 is stood, dry, repetitive operation step 4, thus
Obtain it is a kind of can self-supporting the uniform decorated by nano-gold polystyrene microsphere film of ultrathin, with a thickness of 5 μm, rough surface
Degree is less than 1.5nm, and light transmittance is greater than 86%.
After tested, decorated by nano-gold polystyrene microsphere film comprehensive performance manufactured in the present embodiment is good, can make extensively
With on light, electrical part.This method process flow simultaneously is simple and convenient to operate, is low to environmental factor requirement, and does not cause any
It influences, meets industrial large area, production demand.
Embodiment 3
1, a certain amount of nano-particle carbon is taken to carry out ultrasonic disperse with certain propyl alcohol, concentration is 0.005mg/mL；
2, the resulting nano-particle carbon dispersion liquid of step 1 is sprayed by sprayer with the spray velocity of 500ml/min
The interface of chloroform, in spray process, the size of the drop of sprinkling is 5*10-2Mm, then again by peristaltic pump with 10mL/min
Rate solution is extracted out, so as to form the nano carbon black film with a thickness of 50~300nm；
3, resulting uniform, the transparent nano carbon black film of step 2 is drawn into interfacial liquid by objects such as peristaltic pumps
Method is with the pressure extrusion 30s of 7.5mN/m, the self assembly 10s at 100 DEG C, forms the nano carbon black of conductive uniform, transparent densification
Particle film；
4, the resulting nano-particle carbon film of step 3 is further transferred to any solid interface；
5, the resulting nano-particle carbon film of step 4 is stood, dry, repetitive operation step 4, so that obtaining one kind can
The uniform nano-particle carbon film of the ultrathin of self-supporting, with a thickness of 50nm.
After tested, carbon black pellet film comprehensive performance manufactured in the present embodiment is good, and roughness is less than 1.5nm, transparency
86% can be higher than, conductivity is higher than 500~3000s/m, can be widely used in light, on electrical part.This method process flow simultaneously
It is simple and convenient to operate, is low to environmental factor requirement, and not having any impact, meeting industrial large area, produce need in enormous quantities
It asks.
Embodiment 4
1, the Nano particles of silicon dioxide of a certain amount of nanometer of modified by silver is taken to carry out ultrasonic disperse with certain glycerine, it is dense
Degree is 0.05mg/mL；
2, the Nano particles of silicon dioxide dispersion liquid of resulting nanometer of modified by silver of step 1 is passed through into sprayer with 100ml/
The spray velocity of min is sprayed onto the interface of ionic liquid, and in spray process, the size of the drop of sprinkling is 8*10-2Mm, then again
Solution is extracted out with the rate of 15mL/min by peristaltic pump, the Nano particles of silicon dioxide so as to form nanometer modified by silver is thin
Film；
3, the Nano particles of silicon dioxide film of resulting uniform, the transparent nanometer modified by silver of step 2 is passed through into peristaltic pump
Equal objects draw the method for interfacial liquid with the pressure extrusion 20s of 7.6mN/m, and the self assembly 100s at 80 DEG C is formed conductive equal
The Nano particles of silicon dioxide film of the nanometer modified by silver of even, transparent densification；
4, the Nano particles of silicon dioxide film of resulting nanometer of modified by silver of step 3 is further transferred to any solid circle
Face；
5, the Nano particles of silicon dioxide film of resulting nanometer of modified by silver of step 4 is stood, dry, repetitive operation step
4, thus obtain it is a kind of can self-supporting the uniform nanometer modified by silver of ultrathin Nano particles of silicon dioxide film, with a thickness of
20nm。
After tested, the Nano particles of silicon dioxide film comprehensive performance of nanometer modified by silver manufactured in the present embodiment is good, slightly
Rugosity is less than 1.5nm, and transparency can be higher than 86%, and conductivity is higher than 500~3000s/m, can be widely used in light, electrical part
On.This method process flow simultaneously is simple and convenient to operate, is low to environmental factor requirement, and does not have any impact, and meets industry
Large area, production demand.
Reference examples
This reference examples prepares nano carbon black film using traditional knife coating
1, take a certain amount of nano-particle carbon with certain polymer solution (the triethyl phosphate solution of such as 2%PVDF)
Ultrasonic disperse is carried out, concentration is 0.05mg/mL；
2, the resulting nano-particle carbon dispersion liquid of step 1 is prepared by knife coating in ptfe surface.
3, the resulting nano-particle carbon film of step 2 is stood, it is dry, to obtain a kind of carbon black pellet film, do
The nano carbon black film with a thickness of 5~100um is formd after dry；
4, the resulting nano carbon black film of step 3 is further transferred to any solid interface；
5, the resulting nano-particle carbon film of step 4 is stood, dry, repetitive operation step 4, so that obtaining one kind can
The carbon black pellet laminated film of self-supporting.
After tested, the roughness for the film that this method obtains is greater than 1 μm, and transparency is almost non-conductive lower than 10%, is difficult
Transfer.
By above-mentioned technical proposal, nano/micrometre particle and its modifier film comprehensive performance prepared by the present invention is good
Light can be widely used in, on electrical part；Preparation process flow of the present invention is simple and convenient to operate, is low to environmental factor requirement simultaneously,
And do not have any impact, meet industrial large area, production demand.
In addition, inventor also utilizes the alternate embodiments such as listed other raw materials and other process conditions above
Various raw materials and corresponding process conditions in 1-4 have carried out corresponding test, and obtained ultrathin transparent nano/micron structure self assembly is thin
Pattern, the performance of film etc. are also ideal, substantially similar to 1 product of embodiment.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, those skilled in the art should understand that, to technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (10)
1. a kind of environment-friendly preparation method thereof of ultrathin transparent nano/micron structure self-assembled film, characterized by comprising:
(1) by the modifier of nano/micron structure and/or nano/micron structure be scattered in the first liquid-phase system formed nanometer/
Micrometer structure dispersion liquid；
(2) nano/micron structure dispersion liquid is sprayed to by second liquid phase system surface with spray pattern, is waved to the first liquid-phase system
After hair, then the second liquid phase system is removed, obtains nano/micron structure film；
(3) extrusion process is carried out to the nano/micron structure film using surface tension of liquid, makes the Nano/micron knot
Structure film carries out self assembly on gas-liquid interface and forms form compact and stable nano/micron structure film, obtains structure and uniformly may be used
The nano/micron structure self-assembled film of control；
Wherein, dispersion degree of the modifier of the nano/micron structure and/or nano/micron structure in the first liquid-phase system
Greater than the dispersion degree in second liquid phase system, and the first liquid-phase system cannot dissolve each other with second liquid phase system.
2. preparation method according to claim 1, characterized by comprising: nano/micron structure dispersion liquid to be sprayed to
When second liquid phase system surface, the spray velocity used for 5ml/min~500ml/min, and/or, by nano/micron structure point
When dispersion liquid is sprayed to second liquid phase system surface, the nano/micron structure film of the spray area and preparation of generation at
Membrane area is identical or close；Preferably, in spray process, the size of the drop of sprinkling is 5*10-3Mm~5*10-1mm。
3. preparation method according to claim 1, characterized by comprising: use peristaltic pump pumps mode by described second
Liquid-phase system removes；Preferably, use the rate of second liquid phase system described in peristaltic pump pumps for 5mL/min~20mL/min；
Preferably, the time of the extrusion process is 5s~60s；Preferably, the pressure that the extrusion process uses is 7.2~7.8mN/
m。
4. preparation method according to any one of claim 1-3, it is characterised in that further include step (4): will be described super
Thin transparent nano/micrometer structure self-assembled film is transferred to selected interface and is self-assembly of by different structure nano film layers
The mixed film of layer self assembly；Preferably, the mixed film includes at least one nano/micron structure or Nano/micron knot
The modifier of structure；Preferably, the preparation method further include: circulating repetition carries out step (3) and/or step (4) more than twice,
Until the ultrathin transparent nano/micron structure self-assembled film needed for obtaining；Especially preferred, cycle-index is 5~10 times；It is excellent
Choosing, the specific interface includes solid phase interface or liquid interface.
5. preparation method according to claim 1, it is characterised in that further include: by nano/micron structure and/or nanometer/
The modifier of micrometer structure is added in the first liquid-phase system, carries out ultrasonic disperse, forms nano/micron structure dispersion liquid；It is preferred that
, the time of the ultrasonic disperse is 0.5~20h；Preferably, first liquid-phase system include ethyl alcohol, propyl alcohol, glycerine and
Any one in water or two or more combinations；Preferably, the concentration of the nano/micron structure dispersion liquid is 0.005mg/
ML~2.0mg/mL；
And/or the modifier of the nano/micron structure is by nano/micron structure and modifying agent is blended or graft reaction shape
At；Preferably, the modifier of the nano/micron structure includes organic matter and/or inorganic matter；Preferably, the Nano/micron
The modified group that the modifier of structure includes includes-NH2, any one or two or more combinations in-COOH and-OH.
6. preparation method described in any one of -3,5 according to claim 1, it is characterised in that: the nano/micron structure and/
Or the modifier of nano/micron structure includes one-dimensional material, two-dimensional material or three-dimensional material；Preferably, the Nano/micron knot
The size of at least one dimension of structure and/or the modifier of nano/micron structure is greater than 1 nanometer and less than 1000 microns；With/
Or, the nano/micron structure includes nano/micrometre particle and/or Nano/micron line；Preferably, the Nano/micron grain
Attached bag includes metal nanoparticle, any one in metal and/or nonmetal oxide particle, polymer particle and nano-carbon material
Kind or two or more combinations；Especially preferred, the metal nanoparticle includes nano Au particle and/or nano silver particles；
Especially preferred, the metal and/or nonmetal oxide particle include Nano particles of silicon dioxide, titanium dioxide nano-particle
With any one or the two or more combinations in ferroferric oxide magnetic nano-particles；It is especially preferred, the polymer beads
Attached bag includes polystyrene microsphere；Especially preferred, the nano-carbon material includes appointing in carbon nanotube, graphene and bucky-ball
Meaning a combination of one or more.
7. preparation method according to claim 1, it is characterised in that: the second liquid phase system include water, carbon disulfide,
Any one in chloroform and ionic liquid or two or more combinations；Preferably, the nano/micron structure film is in gas-liquid
Self assembly temperature on interface is 20~100 DEG C, and the time is 10s~1000s.
8. the ultrathin transparent nano/micron structure self-assembled film prepared by any one of claim 1-7 the method；It is preferred that
, the film with a thickness of 20nm~10 μm, surface roughness is less than 1.5nm, and light transmittance is greater than 86%；Preferably, described
Film include the nano/micron structure array being made of the modifier of nano/micron structure and/or nano/micron structure and/or
Nano/micron structure network；Preferably, the modifier of the nano/micron structure is blended by nano/micron structure with modifying agent
Or grafting is formed；Preferably, the modifier of the nano/micron structure includes organic matter and/or inorganic matter；Preferably, described
Nano/micron structure includes nano/micrometre particle and/or Nano/micron line.
9. ultrathin transparent nano/micron structure self-assembled film according to any one of claims 8 is in preparing transparent devices, electrically conducting transparent
Film, super-hydrophobic coat, nanometer or micro ordered array, nanoparticle or nano wire self-assembled material, nano-catalyst material or
Purposes in person's Raman reinforcing material.
10. a kind of device, it is characterised in that include ultrathin transparent nano/micron structure self-assembled film according to any one of claims 8；
Preferably, described device includes Optical devices, electronic device or photoelectron device.
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