CN110371919A - A kind of self-assembly preparation method thereof of micro-nano multistage rod structure - Google Patents
A kind of self-assembly preparation method thereof of micro-nano multistage rod structure Download PDFInfo
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- CN110371919A CN110371919A CN201910654445.4A CN201910654445A CN110371919A CN 110371919 A CN110371919 A CN 110371919A CN 201910654445 A CN201910654445 A CN 201910654445A CN 110371919 A CN110371919 A CN 110371919A
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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
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/04—Networks or arrays of similar microstructural 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
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
Abstract
The present invention provides a kind of self-assembly preparation method thereofs of micro-nano multistage rod structure, are related to technical field of micro nano material preparation.The following steps are included: organic film is deposited on the surface of aluminium base AAO template, then prepolymer is poured into surface, the solidification of aluminium base AAO template, obtain solidified sample；Aluminium base AAO template in erosion removal solidified sample, and with organic solvent washing, obtain the nano column array of organic solvent wetting；Finally pass through precooling and freeze-drying, forms micro-nano multistage rod structure.Organic solvent is converted into gaseous state from solid-state by freeze-drying by the present invention, can reduce influence of the surface tension to nano column array pattern when evaporating in drying process, i.e., nanometer intercolumniation will not mutually pull and cluster obtain it is very tight；By controlling the precooling temperature of organic solvent, the adjusting to nano-pillar self assembly scale size may be implemented.
Description
Technical field
The present invention relates to technical field of micro nano material preparation, and in particular to a kind of self assembly of micro-nano multistage rod structure
Preparation method.
Background technique
Polymer architecture shows in fields such as organic semiconductor device, bio-sensing, bionical adhesive function surfaces in recent years
Broad application prospect is gone out, so how to construct polymer structure system becomes the focus of people's research hot spot.
There is researcher using traditional photoetching technique, receiving for higher resolution is realized by constantly shortening exposure wavelength
Rice photoetching, but processing cost is very high；Be scanned processing also by technologies such as electron beam and focused ion beams, higher cost and
Inefficiency；Also there is researcher to prepare nanostructure using nanometer embossing, but due to being limited by demoulding factor, be difficult to obtain
High-aspect-ratio and the intact nanostructure of structure；Also researcher prepares polymer nanocomposite column array using template method is sacrificed.
But at present in relation to constructing polymer architecture in terms of research be mainly concentrated in through a variety of different methods realize simply
Nano column array, and the multiple dimensioned self assembly to how to further realize nano column array, to construct with specific physical
It limits micro- to the multistage under different scale with the functional assembly system of chemical property there are no mature technique is available
Basic research and application in terms of nano structural material, so how to realize self assembly and the regulation self assembly scale of micro-nano column
Size be urgent problem to be solved.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of self-assembly preparation method thereofs of micro-nano multistage rod structure.This
The micro-nano multistage rod structure that the method that invention provides obtains has self assembly scale Modulatory character.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of self-assembly preparation method thereofs of micro-nano multistage rod structure, comprising the following steps:
After the cleaning of aluminium base AAO template, organic film is deposited on the surface of the aluminium base AAO template, then by prepolymer
It is poured into surface, the solidification of the aluminium base AAO template, obtains solidified sample；The prepolymer is poured into more than the aluminium base AAO
The hole height of holes of template；
By the aluminium base AAO template removal in the solidified sample, nano column array is obtained；
The nano column array obtains the nano column array of organic solvent wetting through organic solvent washing；
Nano column array successively pre-cooled jelly and the freeze-drying of the organic solvent wetting, obtains the micro-nano multistage
Rod structure.
Preferably, the material of the organic film includes Parylene or SBS resin；The organic film with a thickness of
10~50nm.
Preferably, the step of removing aluminium base AAO template includes: that the solidified sample is successively immersed in the first NaOH is molten
Liquid, CuCl2In the mixed solution of HCl, the second NaOH solution.
Preferably, the organic solvent includes acetone, the tert-butyl alcohol, isoamyl acetate or antifreeze protein solution.
Preferably, the temperature of the precooling is lower than the fusing point of the organic solvent.
Preferably, the temperature of the freeze-drying is lower than the fusing point of the organic solvent.
The present invention provides a kind of self-assembly preparation method thereofs of micro-nano multistage rod structure, comprising the following steps: by aluminium base
After the cleaning of AAO template, organic film is deposited on the surface of the aluminium base AAO template, prepolymer is then poured into the aluminium base
The surface of AAO template, solidification, obtain solidified sample；The prepolymer is poured into high more than the hole of the aluminium base AAO template
Degree；By the aluminium base AAO template removal in the solidified sample, nano column array is obtained；The nano column array is through organic solvent
Washing obtains the nano column array of organic solvent wetting；The nano column array of organic solvent wetting successively pre-cooled jelly and
Freeze-drying obtains the micro-nano multistage rod structure.
Organic solvent is converted into gaseous state from solid-state, can be reduced in drying process by the present invention by freeze-drying
Influence of the surface tension to nano column array pattern when evaporating, i.e. nanometer intercolumniation will not be pullled mutually and cluster obtain it is very tight；
By controlling the precooling temperature of organic solvent, the adjusting to nano-pillar self assembly scale size may be implemented.Through the invention
The obtained micro-nano column of micro-nano multistage rod structure of self-assembly preparation method thereof be not adhered, there is excellent performance；Wet glutinous
The fields such as attached surfacing, high sensor, electronics and optical device are with a wide range of applications.The data of embodiment
Show: having certain interval between the nano-pillar in the micro-nano multistage rod structure of present invention gained, no cluster obtains very close.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of aluminium base AAO template, wherein 1 is honeycomb-shaped oxidizing aluminium, and 1-1 is hole, and 1-2 is honeycomb
Shape aluminium oxide upper surface, 2 be aluminium substrate；
Fig. 2 is that the pre-cooled jelly of nano column array soaked from organic solvent and freeze-drying obtain micro-nano multistage rod structure
Schematic diagram；
Fig. 3 is the self-assembly preparation method thereof flow diagram of the micro-nano multistage rod structure of the present invention；
Fig. 4 is the electromicroscopic photograph under embodiment 1 gained, 5200 multiplying power of micro-nano multistage rod structure；
Fig. 5 is the electromicroscopic photograph under embodiment 1 gained, 25000 multiplying power of micro-nano multistage rod structure；
Fig. 6 is the electromicroscopic photograph under embodiment 2 gained, 5200 multiplying power of micro-nano multistage rod structure；
Fig. 7 is the electromicroscopic photograph under embodiment 2 gained, 19000 multiplying power of micro-nano multistage rod structure；
Fig. 8 is the electromicroscopic photograph under embodiment 3 gained, 5200 multiplying power of micro-nano multistage rod structure；
Fig. 9 is the electromicroscopic photograph under embodiment 3 gained, 12500 multiplying power of micro-nano multistage rod structure；
Figure 10 is the electromicroscopic photograph under embodiment 4 gained, 5200 multiplying power of micro-nano multistage rod structure；
Figure 11 is the electromicroscopic photograph under embodiment 4 gained, 12500 multiplying power of micro-nano multistage rod structure.
Specific embodiment
The present invention provides a kind of self-assembly preparation method thereofs of micro-nano multistage rod structure, comprising the following steps:
After the cleaning of aluminium base AAO template, organic film is deposited on the surface of the aluminium base AAO template, then by prepolymer
It is poured into surface, the solidification of the aluminium base AAO template, obtains solidified sample；The prepolymer is poured into more than the aluminium base AAO
The hole height of holes of template；
By the aluminium base AAO template removal in the solidified sample, nano column array is obtained；
The nano column array obtains the nano column array of organic solvent wetting through organic solvent washing；
Nano column array successively pre-cooled jelly and the freeze-drying of the organic solvent wetting, obtains the micro-nano multistage
Rod structure.
After the cleaning of aluminium base AAO template, organic film is deposited on the surface of the aluminium base AAO template, then by prepolymer
It is poured into surface, the solidification of the aluminium base AAO template, obtains solidified sample；The prepolymer is poured into more than the aluminium base AAO
The hole height of holes of template.
The present invention is not specifically limited the size of the aluminium base AAO template, and those skilled in the art are according to actual needs
The micro-nano multistage rod structure of preparation is selected.In the specific embodiment of invention, the aluminium base AAO template it is effective
Thickness is preferably 5 μm, i.e., the depth of hole is 5 μm；Area is preferably 20mm × 20mm；The aperture of hole is preferably 400nm；Hole
The center spacing in hole is preferably 450nm.The present invention is not specifically limited the source of the aluminium base AAO template, using this field
Commercial product known to technical staff.
In the present invention, the step of aluminium base AAO template is cleaned preferably includes: the aluminium base AAO template is successively existed
It is cleaned by ultrasonic in deionized water, ethyl alcohol and acetone；The present invention to the dosage of the deionized water, ethyl alcohol and acetone, wash number,
Ultrasonic power and time are not specifically limited, as long as can remove the impurity of the aluminium base AAO template surface clean.
In the present invention, the material of the organic film is preferably Parylene or SBS resin；The organic film
Thickness is preferably 10~50nm, further preferably 20~40nm, more preferably 30nm.Side of the present invention to vapor deposition organic film
Formula and parameter are not specifically limited, as long as organic film can be deposited.In the present invention, the aluminium base AAO template
Structural schematic diagram is as shown in Figure 1,1 be wherein honeycomb-shaped oxidizing aluminium, 1-1 is hole, and 1-2 is honeycomb-shaped oxidizing aluminium upper surface, and 2 are
Aluminium substrate；For the present invention when organic film is deposited, the organic film is attached on the wall of described hole 1-1 and the honeycomb
Aluminium oxide upper surface (i.e. position shown in 1-2).
In the present invention, it can reduce in aluminium base AAO template surface vapor deposition organic film and be filled in aluminium base AAO template
Physics gluing in hole between the nano column array of polymerizable material.
The present invention is not specifically limited the type of the prepolymer, and those skilled in the art select according to actual needs
It selects, specifically such as: the prepolymer preferably includes thermosetting material and corresponding curing agent, thermoplastic material and corresponding
Curing agent；The thermosetting material preferably includes PDMS or EP, and the thermoplastic material preferably includes PS or PMMA.In the present invention
In, it is also preferable to include corresponding curing agent in the prepolymer.In a specific embodiment of the present invention, the prepolymer includes
PDMS and corresponding curing agent；The mass ratio of the PDMS prepolymer and corresponding curing agent is preferably 10:1.
Prepolymer of the invention is preferably stirred degasification before casting, guarantees that prepolymer component in solidification is uniformly solid
Change.
The present invention is not specifically limited the mode on the surface that the prepolymer is poured into the aluminium base AAO template, adopts
With pouring type well known to those skilled in the art.Prepolymer is poured into the surface of the aluminium base AAO template by the present invention
The step of be particularly preferred as: prepolymer is poured into the hole of the honeycomb-shaped oxidizing aluminium of the aluminium base AAO template, and made described
Prepolymer is poured into more than described hole height；That is, pouring after filling hole when prepolymer is poured, continuing to be poured, make institute
Stating also has certain thickness prepolymer on honeycomb-shaped oxidizing aluminium upper surface (i.e. 1-2 in Fig. 1), the present invention is to the honeycomb oxygen
The thickness for changing the prepolymer of aluminium upper surface is not specifically limited, and has certain thickness.
After casting, it is also preferable to include will be poured product and be placed in vacuum desiccator to vacuumize 20min by the present invention.At this
In invention, vacuumize process can be such that the prepolymer of casting is substantially filled in the hole of aluminium base AAO template.
The present invention is not specifically limited the cured parameter, is set according to the concrete type of selected prepolymer
It sets, specifically such as, when the prepolymer is PDMS prepolymer and corresponding curing agent, the cured temperature is preferably 75
DEG C, the time is preferably 1.5h.Solidification of the invention preferably carries out in an oven.
After obtaining solidified sample, the present invention removes the aluminium base AAO template in the solidified sample, obtains nano-pillar battle array
Column.
In the present invention, the step of removing aluminium base AAO template preferably includes: the solidified sample is successively immersed in first
NaOH solution, CuCl2In the mixed solution of HCl, the second NaOH solution.In the present invention, first NaOH solution and
The concentration of two NaOH solutions is independently preferably 5wt%；The CuCl2With CuCl in the mixed solution of HCl2Mass fraction it is excellent
It is selected as 75%, the mass fraction of the HCl is preferably 15%.
In the present invention, the time that the solidified sample impregnates in the first NaOH solution is preferably 10min；The solidification
After sample impregnates in the first NaOH solution, it is also preferable to include the sample deionized waters after impregnating the first NaOH solution
After flushing, then it is impregnated into next solution.In the present invention, the solidified sample being immersed in the first NaOH solution can go
Except the aluminium oxide in aluminium base AAO template.
In the present invention, the sample after the first NaOH solution dipping is in CuCl2With impregnated in the mixed solution of HCl when
Between preferably 20min；In CuCl2After impregnating in HCl mixed solution, it is also preferable to include by CuCl2It is molten with the mixing of HCl
After sample after liquid dipping is rinsed with deionized water, then it is impregnated into next solution.In the present invention, sample is immersed in CuCl2
In the mixed solution of HCl, the aluminium substrate in aluminium base AAO template can be removed.
In the present invention, through CuCl2With the sample after the mixed solution of HCl dipping impregnated in the second NaOH solution when
Between preferably 10min；After dipping in the second NaOH solution, it is also preferable to include the samples after impregnating the second NaOH solution
It is rinsed with deionized water.In the present invention, sample is immersed in the second NaOH solution, can be by the sightless oxygen of remaining naked eyes
Change aluminium removal.
In the present invention, by after the aluminium base AAO template removal in the solidified sample, preferably make to remove aluminium base AAO template
Sample afterwards is constantly in liquid environment, and the liquid environment is preferably deionized water；Nano column array can be obtained.
After obtaining nano column array, the nano column array through organic solvent washing, is obtained organic solvent profit by the present invention
Wet nano column array.
The present invention is using before organic solvent washing nano column array, and it is also preferable to include by the anhydrous second of nano column array
Alcohol washing, the number and mode that the present invention washs the dehydrated alcohol are not specifically limited, ripe using those skilled in the art
The cleaning parameters and step known, as long as can be by most or all replacements of the liquid environment adhered on nano column array
?.
In the present invention, the organic solvent preferably includes acetone, the tert-butyl alcohol, isoamyl acetate or antifreeze protein solution,
The further preferably tert-butyl alcohol.The present invention is not specifically limited the number and mode of organic solvent washing nano column array.
In the present invention, organic solvent be introduced into be conducive to orderly in subsequent freezing dry process of nano column array and
Regulatable self assembly.
After obtaining the nano column array of organic solvent wetting, nano column array that the present invention soaks the organic solvent according to
Secondary pre-cooled jelly and freeze-drying obtain the micro-nano multistage rod structure.
In the present invention, the temperature of the precooling is preferably shorter than the fusing point of the organic solvent；The temperature of the precooling
Degree is lower, and the micron column diameter being self-assembly of is smaller.In the present invention, the temperature of the freeze-drying is preferably shorter than described has
The fusing point of solvent, prevents organic solvent from melting, and continues freeze-drying until organic solvent distils completely；The freeze-drying
Time be preferably 12h；The freeze-drying preferably carries out under vacuum conditions, the preferably corresponding freeze-drying of the vacuum degree
At a temperature of organic solvent saturated vapour pressure 1/2~1/4.
After freeze-drying, the present invention will be it is also preferable to include that will be freeze-dried product under vacuum conditions, under room temperature
It is cooling, obtain the micro-nano multistage rod structure.
Fig. 2 is that the pre-cooled jelly of nano column array of organic solvent wetting and freeze-drying obtain micro-nano multistage rod structure
Schematic diagram.
Organic solvent is converted into gaseous state from solid-state, can be reduced in drying process by the present invention by freeze-drying
Influence of the surface tension to nano column array pattern when evaporating, i.e. nanometer intercolumniation will not be pullled mutually and cluster obtain it is very tight；
By controlling the precooling temperature of organic solvent, the adjusting to nano-pillar self assembly scale size may be implemented.
Fig. 3 is the self-assembly preparation method thereof flow diagram of the micro-nano multistage rod structure of the present invention, and the present invention is in aluminium base AAO
After the surface casting prepolymer of template, solidification, after removing by aluminium base AAO template and use organic solvent washing, obtain organic molten
The nano column array of agent wetting；The pre-cooled jelly of the nano column array that the organic solvent is soaked and freeze-drying, the nanometer
Column is polymerized to form a micron column, ultimately forms micro-nano multistage rod structure.
It is carried out below with reference to self-assembly preparation method thereof of the embodiment to micro-nano multistage rod structure provided by the invention detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
Step 1: after aluminium base AAO template is successively cleaned by ultrasonic in deionized water, ethyl alcohol and acetone, in the aluminium base
Parylene (Parylene) film is deposited in the surface of AAO template (with a thickness of 50nm)；By the prepolymer of DOW CORNING 184 and admittedly
Agent 10:1's in mass ratio is sufficiently stirred rear degasification, obtains prepolymer；The prepolymer is poured into and described is vapor-deposited with poly- pair
The aluminium base AAO template surface (degree of the polymer fluid casting is more than hole height of holes 5mm) of dimethylbenzene film, then will
It, which is put into vacuum desiccator, vacuumizes 20min, takes out and is placed in the oven heat that temperature is 75 DEG C, be heating and curing 1.5h, obtains
To solidified sample；
Step 2: solidified sample being immersed in the NaOH solution that mass fraction is 5%, stand 10min, take out solidification sample
It is rinsed after product with deionized water；Sample is immersed in the CuCl of mass fraction 70% again2The HCl of solution and mass fraction 15% is molten
In the mixed solution of liquid, 20min is dissolved, it can be seen that acutely, after bubble collapse, aluminium takes out sample by fully reacting for reaction
Product are rinsed with deionized water again；Sample is put into again in the NaOH solution of mass fraction 5%, stands 10min, removal naked eyes
Sightless aluminium oxide；Sample is taken out, is in deionized water environment, obtains nano column array；
Step 3: the nano column array being put into dehydrated alcohol, 15min is stood, reprocessing three times, obtains ethyl alcohol
The polymer nanocomposite column of wetting；The polymer nanocomposite column of ethanol wet is put into pure t-butanol solution, 30 DEG C of water-bath heat preservations
20min is reprocessed 3 times, obtains the nano column array of tert-butyl alcohol wetting；
Step 4: the nano column array that the tert-butyl alcohol soaks is put into liquid nitrogen (- 196 DEG C) precooling 5min, it is then fast
Speed is put into vacuum desiccator, is placed in 4 DEG C of insulating boxs and is vacuumized 12h；Evacuated state is kept, by vacuum desiccator from constant temperature
It is taken out in case, stands 30min at room temperature, after it restores room temperature, taken out, obtain the PDMS that self assembly scale is about 2~5 μm
Micro-nano multistage rod structure.
Fig. 4 is the electromicroscopic photograph under 5200 multiplying power of micro-nano multistage rod structure obtained by the present embodiment；Fig. 5 is the present embodiment institute
Obtain the electromicroscopic photograph under 25000 multiplying power of micro-nano multistage rod structure.As can be seen from Figure 4 and Figure 5: nano column array is dry in freezing
The micron order column structure that many average dimension sizes are 3 μ m, 3 μm of areas, and nanometer have been self-assembly of during dry
There is certain interval between column, no cluster obtains very close.
Embodiment 2
The difference from embodiment 1 is that the nano column array that the tert-butyl alcohol soaks in step 4 is the ice for being -18 DEG C in temperature
Precooling is carried out in case, obtains the micro-nano micro-nano multistage column knot of column array surface of the PDMS that self assembly scale is about 5~10 μm
Structure.
Fig. 6 is the electromicroscopic photograph under 5200 multiplying power of micro-nano multistage rod structure obtained by the present embodiment；Fig. 7 is the present embodiment institute
Obtain the electromicroscopic photograph under 19000 multiplying power of micro-nano multistage rod structure.As can be seen from Figures 6 and 7: nano column array is dry in freezing
The micron order column structure that many average dimension sizes are 6 μ m, 6 μm of areas, and nanometer have been self-assembly of during dry
There is certain interval between column, no cluster obtains very close.
Embodiment 3
The difference from embodiment 1 is that the nano column array that the tert-butyl alcohol soaks in step 4 is the refrigerator for being 4 DEG C in temperature
Middle carry out precooling obtains the micro-nano multistage rod structure of the PDMS that self assembly scale is about 10~15 μm.
Fig. 8 is the electromicroscopic photograph under 5200 multiplying power of micro-nano multistage rod structure obtained by the present embodiment；Fig. 9 is the present embodiment institute
Obtain the electromicroscopic photograph under 12500 multiplying power of micro-nano multistage rod structure.From Fig. 8 and Fig. 9 it can be seen that nano column array is dry in freezing
It has been self-assembly of many average dimension sizes during dry and has been the micron order column structure of 10 μ m, 10 μm of areas, and has received
There is certain interval between meter Zhu, no cluster obtains very close.
Embodiment 4
The difference from embodiment 1 is that the nano column array that the tert-butyl alcohol soaks in step 4 is the refrigerator for being 4 DEG C in temperature
Middle carry out precooling obtains the PDMS nano column array surface micronano multistage rod structure that self assembly scale is about 15~20 μm.
Figure 10 is the electromicroscopic photograph under 5200 multiplying power of micro-nano multistage rod structure obtained by the present embodiment；Figure 11 is the present embodiment
Electromicroscopic photograph under gained 12500 multiplying power of micro-nano multistage rod structure.From Figure 10 and Figure 11 it can be seen that nano column array is cold
The dry micron order column structure for being self-assembly of many average dimension sizes in the process as 15 μ m, 15 μm of areas is lyophilized,
And having certain interval between nano-pillar, no cluster obtains very close.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of self-assembly preparation method thereof of micro-nano multistage rod structure, which comprises the following steps:
After the cleaning of aluminium base AAO template, organic film is deposited on the surface of the aluminium base AAO template, is then poured prepolymer
Surface, solidification to the aluminium base AAO template, obtain solidified sample；The prepolymer is poured into more than the aluminium base AAO template
Hole height of holes；
By the aluminium base AAO template removal in the solidified sample, nano column array is obtained；
The nano column array obtains the nano column array of organic solvent wetting through organic solvent washing；
Nano column array successively pre-cooled jelly and the freeze-drying of the organic solvent wetting, obtains the micro-nano multistage column knot
Structure.
2. self-assembly preparation method thereof according to claim 1, which is characterized in that the material of the organic film includes poly- pair
Dimethylbenzene or SBS resin；The organic film with a thickness of 10~50nm.
3. self-assembly preparation method thereof according to claim 1, which is characterized in that removal aluminium base AAO template the step of include:
The solidified sample is successively immersed in the first NaOH solution, CuCl2In the mixed solution of HCl, the second NaOH solution.
4. self-assembly preparation method thereof according to claim 1, which is characterized in that the organic solvent includes acetone, tertiary fourth
Alcohol, isoamyl acetate or antifreeze protein solution.
5. self-assembly preparation method thereof according to claim 1 or 4, which is characterized in that the temperature of the precooling is lower than institute
State the fusing point of organic solvent.
6. self-assembly preparation method thereof according to claim 1 or 4, which is characterized in that the temperature of the freeze-drying is lower than
The fusing point of the organic solvent.
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| CN113524659A (en) * | 2021-07-14 | 2021-10-22 | 北京航空航天大学 | Method for manufacturing micro-structure conical needle |
| CN115252905A (en) * | 2022-07-14 | 2022-11-01 | 山东第一医科大学(山东省医学科学院) | Bionic material with physical sterilization and immune cell regulation functions and construction method |
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| CN108801513A (en) * | 2017-05-05 | 2018-11-13 | 北京赛特超润界面科技有限公司 | A kind of flexibility stress sensor and preparation method thereof fettering conduction liquid film based on nano wire |
| CN107481920A (en) * | 2017-07-21 | 2017-12-15 | 上海科技大学 | Material and preparation and the application of mechanical stress risers bacterium pattern elongation can be utilized |
| CN109786352A (en) * | 2017-11-14 | 2019-05-21 | 维耶尔公司 | Integrated and bonding of the micro element in system substrate |
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| CN113524659A (en) * | 2021-07-14 | 2021-10-22 | 北京航空航天大学 | Method for manufacturing micro-structure conical needle |
| CN115252905A (en) * | 2022-07-14 | 2022-11-01 | 山东第一医科大学(山东省医学科学院) | Bionic material with physical sterilization and immune cell regulation functions and construction method |
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