CN110128685A - A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film - Google Patents
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film Download PDFInfo
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Abstract
The present invention provides a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, belongs to technical field of nano-processing.The method of the present invention uniquely uses the mixed solution of n-butyl alcohol and ethyl alcohol to carry out the PS microspheres solution of diluting high-concentration, solves the problem of having a big chunk PS microballoon that can sink to liquid level or less with the diffusion of solution after due to dehydrated alcohol and water there is fabulous intersolubility, PS microspheres solution to be added drop-wise in the activator solution of reaction generation container in conventional method and the microballoon film overwhelming majority of preparation is made to be still the double-deck even multilayered structure；And a small amount of NaCl is added in the dilution of PS microballoon to reduce electrostatic force between microballoon, sinks to subsurface PS microballoon quantity to be reduced to, further increase quality of forming film.The contact shape for controlling syringe and activator solution surface in preparation process, makes PS microballoon be self-assembly of the single layer structure of large-area high-quality by this way.
Description
Technical field
The invention belongs to technical field of nano-processing, and in particular to a kind of large-area high-quality single layer PS microballoon film it is molten
Liquid self-assembling method.
Background technique
Surface with ordered nano-structure is received significant attention because of its unique surface characteristic, and in antireflection, life
Object and chemical sensitisation, absorbent, Surface enhanced Raman scattering (SERS), surface wettability, surface assisted laser desorption/ionogen
The technical fields such as spectrum (SALDI-MS) have broad application prospects.Although photoetching, electron beam lithography, focused-ion-beam lithography,
The advanced processing technology such as soft lithographic, nano impression can also process high-precision ordered nano-structure array, but it is each
Comfortable working (finishing) area, process costs and its complexity etc. receive serious limitation, in large-scale practical preparation side
Face still has extremely challenging.
In recent years, with the development of colloid science, particle diameter distribution is narrow, phase stability is good polystyrene (PS) high monodisperse
The preparation process of colloidal spheres solution is mature, and the diameter of PS microballoon can in tens microns to tens nanometer ranges into
Row is accurate to be adjusted, better than the resolution limit of traditional photoetching and the methods of nano impression.Under suitable condition, this colloid
Ball can be self-assembled into two-dimentional (2D) and three-dimensional (3D) structure can be further in conjunction with subsequent dry or wet etch technology
Process the two and three dimensions nano-structure array such as cone, pyramid, column, hole, ring.Therefore, the single layer of large-area high-quality
The preparation of PS microballoon film is the premise of colloid photoetching technique, is of great significance to the ideal structure of acquisition and performance.It is closed
Key be how using suitable physics and chemical method come the period of accuracy controlling PS microballoon, arrangement mode and size and shape
The forms such as shape, so that the nanostructure processed has flexible adjustability.
The solution aggregation and spin coating self assembly that German M.Giersig [1] and Ulrich Jonas [2] et al. successively propose
Method exists in terms of process controllability, microballoon although local single layer PS microballoon film can be prepared
Serious deficiency is unable to get the large area single layer PS film of high quality.The Petros I.Stavroulakis [3] of Britain is logical
It crosses the substrate that will be laid flat and is changed to 10 ° of inclination, and replace czochralski method with evaporation, thus improving film quality to a certain degree,
But still there is significant portion of double-layer film structure.The Japanese Tadaaki Nagao of Kai Chen and the U.S. et al. [4]
The double-deck PS microballoon self-assembling technique of proposition has shown good controllability, but has no in terms of large area single layer self assembly
Compared with quantum jump.Japanese Scientists Kei Shinotsuka et al. [5] propose ultrasonic wave added and swing assisted self assembling side
Method, although improving the quality of partial mono-layer PS microballoon film, uniformity and compactness over a large area is still insufficient.
The same year, [6] people such as Yi Cui and Jichun Ye propose a kind of microinjection for manufacturing large-area high-quality single layer PS microballoon film
Technique has shown huge application potential in photovoltaic industry, but the technique, there are serious deficiency, injection rate is
0.5ml/h, one piece of 1.7m can be paved with by needing 25 microinjection systems to work at the same time four hours2Substrate, and then produce effect
Rate is low, and process costs are high.It would therefore be highly desirable to develop new process technology scheme on the basis of prior art technology to break through this
One limitation, with simple technique, lower cost, higher efficiency system for the single layer PS microballoon film of column large-area high-quality.
[1]Rybczynski,J.,et al.(2003).Large-scale,2D arrays of magnetic
nanoparticles.Colloids and Surfaces A:Physicochemical and Engineering Aspects
219(1-3):1-6.
[2]Retsch,M.,et al.(2009).Fabrication of Large-Area,Transferable
Colloidal Monolayers Utilizing Self-Assembly at the Air/Water
Interface.Macromolecular Chemistry and Physics 210(3-4):230-241.
[3]Stavroulakis,P.I.,et al.(2009).mproved deposition of large scale
ordered nanosphere monolayers via liquid surface self-assembly.Materials
Science and Engineering:B 165(3):186-189.
[4]Chen,K.,et al.(2015).MoiréNanosphere Lithography.ACS Nano 9(6):
6031–6040.
[5]Shinotsuka,K.,et al.(2015).Crystal Perfection of Particle
Monolayer at the Air-Water Interface.Langmuir 31(42):11452-11457.
[6]Gao,P.,et al.(2015).Large-Area Nanosphere Self-Assembly by a
Micro-Propulsive Injection Method for High Throughput Periodic Surface
Nanotexturing.Nano Letters 15(7):4591-4598.
Summary of the invention
For the problems of background technique, the purpose of the present invention is to provide a kind of large-area high-quality single layer PS is micro-
The solution self-assembling method of ball film, the advantages such as this method has simple process, at low cost, high-efficient, film quality is good.
To achieve the above object, technical scheme is as follows:
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, comprising the following steps:
Step 1: substrate being sequentially placed into acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic；
Step 2: by the substrate and reaction generation container progress ultra-hydrophilic surface processing after step 1 cleaning；
Step 3: mass concentration greater than 1.5% polystyrene (PS) microballoon monodisperse liquor in be added n-butyl alcohol and
The mixed solution A of dehydrated alcohol is diluted, until the mass concentration of PS microballoon is 0.5%~1.5%, obtains mixed solution B；
Step 4: NaCl being added in the mixed solution B described in step 3 and is ultrasonically treated to obtain mixed solution C；
Step 5: substrate is placed in reaction generation container, the activator solution of 4-6 μ L is added in reaction generator,
Solution C is added drop-wise to reaction generation container with the rate less than 0.5ml/min by the mixed solution C described in syringe extraction step 4
In, it scatters rapidly until the PS microspheres solution being added dropwise is no longer along liquid level and directly sinks to liquid level hereinafter, being then allowed to stand 10-30min,
Wherein, the contact surface of syringe and activator solution is kept in contact interface in meniscus shape；
Step 6: the solution in generation container will be reacted after step 5 self-assembling reaction to be extracted out, it is then close with perforated membrane
Envelope reaction generation container, is placed on being dried in drying box, after drying process at a temperature of 80-100 DEG C
Heat treatment 5-10min is carried out, after reaction cooled to room temperature, required single layer PS microballoon film can be prepared.
Further, substrate described in step 1 is inorganic material or organic material, and inorganic material is preferably monocrystalline silicon, glass
Glass, quartz, GaAs, GaN, Si3N4, SiC etc., organic material is preferably PDMS, PMMA etc..
Further, the ultra-hydrophilic surface of substrate described in step 2 handles specific steps are as follows: substrate is immersed 80 DEG C
H2O/H2O2/NH420-40min is handled in the mixed solution of OH；The reaction generation container is placed in UV ozone processing cleaning machine
Middle 15-30min carries out ultra-hydrophilic surface processing.
Further, the volume ratio of n-butyl alcohol and dehydrated alcohol is 3:2~4:1 in mixed solution A described in step 3.
Further, the mass concentration of NaCl is 10mg/mL in mixed solution C described in step 4.
Further, activator solution described in step 5 is lauryl sodium sulfate aqueous solution, wherein dodecyl sulphur
The mass concentration range of sour sodium is 2%~4%.
Further, perforated membrane described in step 6 is microporous freshness-keeping film or porous tinfoil etc..
The operation principle of the present invention is that: (1) it self-assembling reaction after needs to react the solution in generation container and takes out
Out, when solution will be drained, if substrate and removing vessel surface do not carry out any hydrophilic treated, solution will be by
It gradually is gathered into the drop containing PS microballoon toward substrate surface central area, can not only form the single layer PS micro-sphere array of high quality
Structure, and entire substrate surface can not be made by PS microballoon uniform fold；(2) the traditional dilute side of high concentration PS microspheres solution
Method is carried out using the mixed solution of dehydrated alcohol and water, although dispersibility of the PS microballoon in dehydrated alcohol and water is fabulous,
But since dehydrated alcohol and water have fabulous intersolubility in this method, PS microspheres solution is added drop-wise to the work of reaction generation container
After in property agent solution, liquid level can be sunk to the diffusion of solution hereinafter, therefore by having a big chunk PS microballoon, the party
Although PS micro-sphere array prepared by method has the single layer structure of many parts, but the overwhelming majority is still the double-deck even multilayer knot
Structure；And using the mixed solution of n-butyl alcohol and ethyl alcohol come the PS microspheres solution of diluting high-concentration in the present invention, it is because of n-butyl alcohol
It is very poor with the compatibility of water, be added drop-wise to after liquid level will not be because of intersolubility the problem of and so that PS microballoon is sunk to liquid level hereinafter, and
It is to form one layer in liquid level drawout to be coated with the n-butyl alcohol film of PS microballoon, to make PS microballoon in liquid level gradually self assembly shape
At monofilm, and it is fairly insoluble that the monodisperse liquid for solving the problems, such as PS microballoon, which is added, with n-butyl alcohol in ethyl alcohol；Meanwhile the present invention exists
A small amount of NaCl is added in the dilution of PS microballoon to reduce electrostatic force between microballoon, thus be reduced to sink to it is subsurface
PS microballoon quantity；(3) syringe is just contacted with activator solution surface, will form the liquid bridge of meniscus shape, and PS microballoon passes through
The liquid bridge is continuously injected into the single layer structure that large-area high-quality is gradually self-assembly of in the aqueous solution of glassware；
If syringe needle, which is located at liquid level, sinks to subsurface PS microballoon quantity hereinafter, will increase；If syringe needle is located at ullage, PS microspheres solution
It will be entered in a manner of drop in the aqueous solution of glassware, can not only generate apparent convection current impact phenomenon and influence to stablize
Self assembling process, also the blank area largely without PS microballoon can be generated due to this discontinuous self assembly mode.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1, this method is highly concentrated to dilute by the mixed solution using unique chemical reagent, that is, n-butyl alcohol and dehydrated alcohol
The mode of Monodisperse Polystyrene Microspheres solution is spent to regulate and control PS microballoon in the dispersion process and self assembling process of liquid level, is avoided due to portion
The formation of large area bilayer and multilayered structure array caused by dividing PS microballoon to sink, improves PS microballoon in the entirety of substrate surface
Quality of forming film.
2, it joined a small amount of NaCl particle in the dilution of PS microballoon in the present invention to reduce electrostatic between microballoon
Power sinks to subsurface PS microballoon quantity to reduce, so that finally prepd single film layer is preferable.
3, the hexagonal structure of large area single layer PS micro-sphere array of the method for the present invention preparation, was conducive at subsequent quarter
Orderly and uniform large-area nano-structure array is obtained in erosion processing, to significantly improve the performance of all kinds of opto-electronic devices.
Detailed description of the invention
Fig. 1 is the material object of PS microballoon film prepared whether substrate is through super hydrophilic processing in embodiment 1 and comparative example 1
Figure；
Wherein, (a) is PS microballoon film pictorial diagram prepared by embodiment 1；(b) the PS microballoon film prepared for comparative example 1
Pictorial diagram.
Fig. 2 is the pictorial diagram of PS microballoon film prepared by self assembly mode different in embodiment 2 and comparative example 2；
Wherein, (a) is PS microballoon film pictorial diagram prepared by embodiment 2；(b) the PS microballoon film prepared for comparative example 2
Pictorial diagram.
Fig. 3 is the pictorial diagram of the prepared PS microballoon film of chemical reagent dilution different in embodiment 3 and comparative example 3；
Wherein, (a) is PS microballoon film pictorial diagram prepared by embodiment 3；(b) the PS microballoon film prepared for comparative example 3
Pictorial diagram.
Fig. 4 is that 4 large area PS microballoon film pictorial diagram of embodiment and microcosmic SEM scheme；
Wherein, the monocrystal silicon substrate surface PS microballoon film pictorial diagram that (a) is 2 inches；It (b) is 2 inches of monocrystal silicon substrates
The SEM of surface PS microballoon film schemes.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below with reference to embodiment and attached drawing, to this hair
It is bright to be described in further detail.
Embodiment 1
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, specifically includes the following steps:
Step 1: 12 × 2cm monocrystalline silicon being sequentially placed into acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic
10min takes out and with being dried with nitrogen；
Step 2: the monocrystalline silicon after step 1 cleaning is immersed to 80 DEG C of H2O/H2O2/NH4It is handled in the mixed solution of OH
40min, to obtain ultra-hydrophilic surface, wherein H2O、H2O2With NH4The volume ratio of OH is 5:1:1；By the glass of self assembly
Vessel are placed in processing 20min in UV ozone processing cleaning machine and take out to obtain ultra-hydrophilic surface；
Step 3: by 0.5mL mass concentration be 2.5% PS microballoon the monodisperse liquor n-butyl alcohol of 0.4mL and
It is 1% that the mixed solution of 0.25mL dehydrated alcohol, which is diluted to the mass concentration of PS microballoon, and the NaCl of 10mg then is added simultaneously
It is ultrasonically treated 10min；
Step 4:, by monocrystalline silicon be placed in reaction generation container in, lauryl sodium sulfate is added in reaction generator
Aqueous solution, it is using the syringe with syringe needle that the PS microspheres solution after dilution is slow with the rate of 0.4ml/min by liquid bridge
It is injected into the glassware for fill lauryl sodium sulfate aqueous solution and carries out self assembly, stand 20min again after forming a film completely
The aqueous solution in glassware is slowly drained, so that the single layer PS micro-sphere array that solution surface self assembly is completed is transferred directly to
Substrate surface；
Step 5: sealing above-mentioned glassware with porous preservative film and be placed in 60 DEG C of baking oven or drying box and done
Temperature is then increased to 100 DEG C and carries out heat treatment 5min, naturally cools to room after reaction by dry processing 120min
Required single layer PS microballoon film can be prepared in temperature.
Shown in PS microballoon film pictorial diagram such as Fig. 1 (a) manufactured in the present embodiment.
Comparative example 1
Single layer PS microballoon film is prepared according to the step of embodiment 1, only by the monocrystal silicon substrate in step 2 without surface
Super hydrophilic processing, other steps are constant.Shown in PS microballoon film pictorial diagram such as Fig. 1 (b) of this comparative example preparation.
Embodiment 2
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, specifically includes the following steps:
Step 1: 12 × 2cm monocrystalline silicon is sequentially placed into acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic 5min,
It takes out and uses and be dried with nitrogen；
Step 2: the monocrystalline silicon after step 1 cleaning is immersed to 80 DEG C of H2O/H2O2/NH4It is handled in the mixed solution of OH
30min, to obtain ultra-hydrophilic surface, wherein H2O、H2O2With NH4The volume ratio of OH is 5:1:1；By the glass of self assembly
Vessel are placed in processing 15min in UV ozone processing cleaning machine and take out to obtain ultra-hydrophilic surface；
Step 3: by 0.5mL mass concentration be 2.5% PS microballoon the monodisperse liquor n-butyl alcohol of 0.4mL and
It is 1% that the mixed solution of 0.25mL dehydrated alcohol, which is diluted to the mass concentration of PS microballoon, and the NaCl of 10mg then is added simultaneously
It is ultrasonically treated 10min；
Step 4:, monocrystalline silicon is placed in glassware, it is water-soluble that lauryl sodium sulfate is added in reaction generator
PS microspheres solution after dilution is slowly injected by liquid bridge using the syringe with syringe needle and fills dodecyl sulphate by liquid
Self assembly is carried out in the glassware of sodium water solution, and 30min is stood after forming a film completely and slowly drains the water in glassware again
Solution, so that the single layer PS micro-sphere array that solution surface self assembly is completed is transferred directly to substrate surface；
Step 5: sealing above-mentioned glassware with porous preservative film and be placed in 60 DEG C of baking oven or drying box and done
Temperature is then increased to 80 DEG C and carries out heat treatment 10min, after reaction cooled to room temperature by dry processing 90min,
Required single layer PS microballoon film can be prepared.
Shown in PS microballoon film pictorial diagram manufactured in the present embodiment such as Fig. 2 (a).
Comparative example 2
Single layer PS microballoon film is prepared according to the step of embodiment 2, only contacts the syringe needle in step 4 with liquid level
It forms liquid bridge and carries out injection and be adjusted to syringe needle and be located at ullage, PS microspheres solution is distributed to glass by way of being slowly added dropwise
In the aqueous solution of glass vessel, other steps are constant.Shown in PS microballoon film pictorial diagram such as Fig. 2 (b) of this comparative example preparation.
Embodiment 3
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, specifically includes the following steps:
Step 1: 12 × 2cm monocrystalline silicon is sequentially placed into acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic 5min,
It takes out and uses and be dried with nitrogen；
Step 2: the monocrystalline silicon after step 1 cleaning is immersed to 80 DEG C of H2O/H2O2/NH4It is handled in the mixed solution of OH
30min, to obtain ultra-hydrophilic surface, wherein H2O、H2O2With NH4The volume ratio of OH is 5:1:1；By the glass of self assembly
Vessel are placed in processing 25min in UV ozone processing cleaning machine and take out to obtain ultra-hydrophilic surface；
Step 3: by 0.5mL mass concentration be 2.5% PS microballoon the monodisperse liquor n-butyl alcohol of 0.4mL and
It is 1% that the mixed solution of 0.25mL dehydrated alcohol, which is diluted to the mass concentration of PS microballoon, and the NaCl of 10mg then is added simultaneously
It is ultrasonically treated 10min；
Step 4:, monocrystalline silicon is placed in glassware, it is water-soluble that lauryl sodium sulfate is added in reaction generator
PS microspheres solution after dilution is slowly injected by liquid bridge using the syringe with syringe needle and fills dodecyl sulphate by liquid
Self assembly is carried out in the glassware of sodium water solution, and 30min is stood after forming a film completely and slowly drains the water in glassware again
Solution, so that the single layer PS micro-sphere array that solution surface self assembly is completed is transferred directly to substrate surface；
Step 5: sealing above-mentioned glassware with porous preservative film and be placed in 60 DEG C of baking oven or drying box and done
Temperature is then increased to 80 DEG C and carries out heat treatment 10min, after reaction cooled to room temperature by dry processing 90min,
Required single layer PS microballoon film can be prepared.
Shown in PS microballoon film pictorial diagram manufactured in the present embodiment such as Fig. 3 (a).
Comparative example 3
Prepare single layer PS microballoon film according to the step of embodiment 3, only by the diluting condition in step 3 be adjusted to by
The mixing of the monodisperse liquor for the PS microballoon that 0.5mL mass concentration is 2.5% dehydrated alcohol and 0.3mL ultrapure water of 0.3mL
Solution is diluted, other steps are constant.Shown in PS microballoon film pictorial diagram such as Fig. 3 (b) of this comparative example preparation.
Embodiment 4
A kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, specifically includes the following steps:
Step 1: 12 inches of monocrystalline silicon being sequentially placed into acetone, dehydrated alcohol and deionized water and is cleaned by ultrasonic
5min takes out and with being dried with nitrogen；
Step 2: the monocrystalline silicon after step 1 cleaning is immersed to 80 DEG C of H2O/H2O2/NH4It is handled in the mixed solution of OH
30min, to obtain ultra-hydrophilic surface, wherein H2O、H2O2With NH4The volume ratio of OH is 5:1:1；By the glass of self assembly
Vessel are placed in processing 25min in UV ozone processing cleaning machine and take out to obtain ultra-hydrophilic surface；
Step 3: by 0.5mL mass concentration be 2.5% PS microballoon the monodisperse liquor n-butyl alcohol of 0.4mL and
It is 1% that the mixed solution of 0.25mL dehydrated alcohol, which is diluted to the mass concentration of PS microballoon, and the NaCl of 10mg then is added simultaneously
It is ultrasonically treated 10min；
Step 4:, monocrystalline silicon is placed in glassware, it is water-soluble that lauryl sodium sulfate is added in reaction generator
PS microspheres solution after dilution is slowly injected by liquid bridge using the syringe with syringe needle and fills dodecyl sulphate by liquid
Self assembly is carried out in the glassware of sodium water solution, and 30min is stood after forming a film completely and slowly drains the water in glassware again
Solution, so that the single layer PS micro-sphere array that solution surface self assembly is completed is transferred directly to substrate surface；
Step 5: sealing above-mentioned glassware with porous preservative film and be placed in 60 DEG C of baking oven or drying box and done
Temperature is then increased to 80 DEG C and carries out heat treatment 10min, after reaction cooled to room temperature by dry processing 90min,
Required single layer PS microballoon film can be prepared.
Shown in PS microballoon film pictorial diagram manufactured in the present embodiment such as Fig. 4 (a), shown in SEM scanning figure such as Fig. 4 (b).
Fig. 1 is the material object of PS microballoon film prepared whether substrate is through super hydrophilic processing in embodiment 1 and comparative example 1
Figure.Wherein, Fig. 1 (a) shows to obtain using method of the invention in all areas of the silicon chip surface Jing Guo super hydrophilic processing
Good PS microballoon membrane structure；Fig. 1 (b) shows the silicon chip surface without any surface treatment, although intermediate partial zones
Domain has also been self-assembly of preferable PS microballoon membrane structure, but silicon chip edge but has the white space of large area, and
The case where multilayer PS microballoon stacks is locally present.
Fig. 2 is the pictorial diagram of PS microballoon film prepared by self assembly mode different in embodiment 2 and comparative example 2.Its
In, Fig. 2 (a) shows passing through liquid bridge successively and slowly by PS microballoon implantation glass vessel water using method of the invention
The mode of solution obtains perfect membrane structure；Fig. 2 (b) shows then be formed in silicon chip surface by way of being slowly added dropwise
White space of the large area without PS microballoon, so that continuous, complete membrane structure can not be self-assembly of.
Fig. 3 is the pictorial diagram of the prepared PS microballoon film of chemical reagent dilution different in embodiment 3 and comparative example 3.
Wherein, Fig. 3 (a) shows the mixed solution diluting high-concentration using method of the invention by using n-butyl alcohol, ethyl alcohol and NaCl
Monodisperse Polystyrene Microspheres solution can go out the large area single layer PS micro-sphere array that be evenly distributed with self assembly；Fig. 3 (b) shows using biography
The PS micro-sphere array of the PS microballoon dispersion liquid preparation of the dehydrated alcohol and water diluting high-concentration of system is unevenly distributed.
Fig. 4 is that 4 large area PS microballoon film pictorial diagram of embodiment and microcosmic SEM scheme, and shows to utilize this from figure (a) and (b)
The method of invention can form the single layer PS microballoon film of large-area high-quality in the Si piece surface self-organization of wafer scale, and have
There is array structure.
The above description is merely a specific embodiment, any feature disclosed in this specification, except non-specifically
Narration, can be replaced by other alternative features that are equivalent or have similar purpose；Disclosed all features or all sides
Method or in the process the step of, other than mutually exclusive feature and/or step, can be combined in any way.
Claims (8)
1. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film, which comprises the following steps:
Step 1: ultrasonic cleaning substrate；
Step 2: by the substrate and reaction generation container progress ultra-hydrophilic surface processing after step 1 cleaning；
Step 3: n-butyl alcohol and anhydrous being added in the monodisperse liquor of polystyrene (PS) microballoon of mass concentration greater than 1.5%
The mixed solution A of ethyl alcohol is diluted, until the mass concentration of PS microballoon is 0.5%~1.5%, obtains mixed solution B；
Step 4: NaCl being added in the mixed solution B described in step 3 and is ultrasonically treated to obtain mixed solution C；
Step 5: substrate being placed in reaction generation container, activator solution is added in reaction generator, is taken out with syringe
Mixed solution C described in step 4 is taken, solution C is added drop-wise in reaction generation container with the rate less than 0.5ml/min, until being added dropwise
PS microspheres solution be no longer along liquid level and scatter rapidly and directly sink to liquid level hereinafter, being then allowed to stand 10-30min, wherein injection
The liquid level of device and activator solution is kept in contact；
Step 6: after step 5 self-assembling reaction, the solution in generation container will be reacted and extracted out, seal reaction hair with perforated membrane
Raw container, is placed on being dried in drying box, be then heat-treated, and is heat-treated natural cooling after reaction
To room temperature, required single layer PS microballoon film can be prepared.
2. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
It is, substrate described in step 1 is inorganic material or organic material.
3. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as claimed in claim 2, feature
It is, the inorganic material is monocrystalline silicon, glass, quartz, GaAs, GaN, Si3N4Or SiC, the organic material be PDMS or
PMMA。
4. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
It is, substrate ultra-hydrophilic surface described in step 2 handles specific steps are as follows: the substrate is immersed to 80 DEG C of H2O/H2O2/NH4OH
Mixed solution in handle 20-40min；The reaction generation container is placed in UV ozone processing cleaning machine and handles 15-
30min。
5. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
It is, the volume ratio of n-butyl alcohol and dehydrated alcohol is 3:2~4:1 in mixed solution A described in step 3.
6. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
It is, the mass concentration of NaCl is 10mg/mL in mixed solution C described in step 4.
7. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
It is, activator solution described in step 5 is lauryl sodium sulfate aqueous solution, and volume is 4-6 μ L, wherein dodecyl sulphate
The mass concentration range of sodium is 2%~4%.
8. a kind of solution self-assembling method of large-area high-quality single layer PS microballoon film as described in claim 1, feature
Be, perforated membrane described in step 6 be microporous freshness-keeping film or porous tinfoil, the heat treatment process be at a temperature of 80-100 DEG C into
Row 5-10min processing.
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