CN106093004B - Super-hydrophobic molecule enrichment concentration chip and its preparation method and application - Google Patents
Super-hydrophobic molecule enrichment concentration chip and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of super-hydrophobic molecule enrichment concentration chips and its preparation method and application, and the preparation method includes the following steps：The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, is then toasted；The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, it is exposed processing after the completion of contraposition, then development treatment is carried out, deep silicon etching processing then is carried out to silicon chip, then crystal film Au is injected on the silicon chip of silicon column array structure by magnetron sputtering and obtains mould material；Using the graphite cleaned up as cathode, mould material is placed in electrodeposit reaction in electrodeposit liquid and obtains the chip with nano silver silicon column array structure, cleaned up with clear water after taking-up, then dried up with pure argon as anode.The super-hydrophobic molecule enrichment concentration chip prepared has the advantages of hypersensitive, fast-response, low solvent loss rate.
Description
Technical field
The present invention relates to a kind of preparation methods of super-hydrophobic chip, and in particular to a kind of super-hydrophobic molecule enrichment concentration core
Piece and its preparation method and application.
Background technology
Surface enhanced Raman scattering (Surface Enhanced Raman Scattering, call SERS in the following text) technology, be
It finds the 1970s, a kind of new type of high sensitivity spectral analysis technique that mature is got up after the nineties.SERS technologies
Basis be the raman spectral signal of material molecule in specific metal nano material (such as nano-particle of gold, silver, copper
The surface (Nanoparticles, NPs) can be greatly enhanced (106~1010Times).In brief, the protrusion of SERS technologies is excellent
Point shows three aspects：1) there is high sensitivity, unimolecule SERS analyses to have had wide coverage；2) with infrared spectrum phase
Seemingly, can be used for substance qualitative analysis, i.e., in addition to how many can be answered the problem of, can also be true according to the SERS spectra of substance
Surely what is；3) it may be implemented portable without sacrificing analytical performance.In addition, SERS spectra half-peak breadth is only 1nm or so, Duo Zhongfen
It is not susceptible to interfere between substance when analysis object detects simultaneously.
Currently, the relevant report of SERS base material preparation methods be mainly based upon micro-nano structure construct and metal nano
Materials synthesis and the SERS substrates and detection method developed.However, although SERS technologies obtain good development, Metal Substrate system
It is standby also to reach its maturity, but there is also a problems：The preparation process of the metallic matrix of general high enhancement factor is more complicated,
The necessary large scale stable homogeneous of active matrix pattern is sought, and the size of single nanotopography is in nanometer scale or even several nanometers
When magnitude, strong local electromagnetic field could be generated, to cause strong SERS effects.However, prevailing experimental conditions are not easy to operate
With regulation and control, it is difficult to synthesize several nanometer scales and the uniform metal nano material of structure in common lab.In recent years, with electricity
The development of sub-information technology, photoetching technique, which becomes, prepares SERS substrates, builds a kind of important method of nano-array.The technology can
To obtain highly homogeneous nano-array, to obtain the SERS signal of high efficiency high stable.Its stability is current other technologies
It is temporarily incomparable.
However, SERS technologies have certain difficulty for the determinand detection of super low concentration at present, reason is：(1) molecule
Solution excessively dilutes under super low concentration, and molecule adsorption efficiency is very low when being transferred to SERS substrate surfaces, and readily diffuses into base
Each region of bottom material, when actual detection are difficult often quickly and accurately to obtain signal, and difficulty is increased for actual detection.
(2) in actual detection, determinand often exists with solution state, and solution is needed to its volume, concentration, and quantity of solvent carries out accurate
It determines.It is then soaked in solution to be measured with SERS substrates again, entire pretreatment process at least needs 30min, solvent to be also required to
Several milliliters to hundreds of milliliters are differed, time-consuming and laborious.
Currently, the detection technique for super low concentration substance mostly has some disadvantages, desired effect is not fully reached,
Meets the needs of being detected in real work.Therefore, develop highly sensitive, fast-response, low solvent consume, the lossless SERS detections of trace
Technology, it appears particularly important.
Invention content
The object of the present invention is to provide the super-hydrophobic molecule enrichment of a kind of hypersensitive, fast-response, low solvent loss rate is dense
Shrinking chip, the chip can solve the problems, such as that current simple process can not obtain highly sensitive substrate.
It is a further object to provide a kind of preparation methods of super-hydrophobic molecule enrichment concentration chip.
A further object of the present invention is to provide a kind of application of super-hydrophobic molecule enrichment concentration chip in SERS.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme：
A kind of preparation method of super-hydrophobic molecule enrichment concentration chip, includes the following steps：
Step A：The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, then into
Row baking；The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, contraposition is completed laggard
Then row exposure-processed carries out development treatment, obtain the silicon chip of equal one array architecture pattern, and then carrying out deep silicon to silicon chip carves
Erosion is handled, and obtains the silicon chip of uniform silicon column array structure, then crystal film Au is injected in silicon column array structure by magnetron sputtering
Silicon chip on obtain mould material；
Step B：The silver nitrate aqueous solution and 3~5g/L aqueous citric acid solutions of 1~3g/L is 1 according to volume ratio：1 ratio
It mixes uniformly, obtains electrodeposit liquid；Using the graphite cleaned up as cathode, mould material is placed in described as anode
Electrodeposit reaction obtains the chip with nano silver silicon column array structure in electrodeposit liquid, is cleaned up with clear water after taking-up, then
It is dried up with pure argon, obtains the super-hydrophobic molecule enrichment concentration chip.
Further technical solution is that the gap of silicon column and silicon column is 2~5 micro- in the silicon chip of the silicon column array structure
Rice；Silicon column length is 10~50 microns；Pattern magnitude on the photolithography plate is not less than 2.0cm × 2.0cm.
Further technical solution is a diameter of 0.5~0.6cm of the graphite, and the length of graphite is 3~6cm.
Further technical solution is that the electric current of the magnetron sputtering is 25~35mA, and the time of magnetron sputtering is 80
~100s.
Further technical solution is that the electrodeposit reaction is the current response 2~6 in the case where electric current is 200~800mA
Hour.
The present invention provides what the preparation method using the super-hydrophobic molecule enrichment concentration chip was prepared to surpass
Hydrophobic molecule enrichment concentration chip, is square or the nano silver silicon column that hexagon uniform array lattice structure arranges, institute
The nano silver silicon column stated is that nano silver is uniformly wrapped up in silicon column, the lamellar structure that nano silver is 1~2 micron, and nano silver silicon column is
Highly 12~55 microns, a diameter of 2~5 microns of regular column, the gap between nano silver silicon column are 8~12nm.
Further technical solution is that the super-hydrophobic molecule enrichment concentration chip has super-hydrophobic effect, with water
Contact angle >=140 °.
The present invention also provides the super-hydrophobic molecule enrichments to concentrate application of the chip in SERS, including following step
Suddenly：It is with plasma cleaning instrument that the citric acid cleaning for remaining in super-hydrophobic molecule enrichment concentration chip surface is clean, then will
The super-hydrophobic molecule enrichment concentration chip cleaned up is put on the table, and 3~5 microlitres of testing liquids is taken to drop in chip surface,
5~8 minutes are stood, the trace left after observation drop evaporation is enriched with enrichment region with confocal laser Raman spectrometer to drop
Domain is focused acquisition, carries out SERS detections.
Further technical solution is, testing liquid is to be dissolved in water or explosive not soluble in water, organic pollution, organic
One kind in dyestuff, drug molecule.
Further technical solution is, when the testing liquid is liquid not soluble in water, to be carried out to testing liquid
Acidification or alkalization become soluble-salt and are detected again.
The present invention will be further explained below.
The preparation method of the present invention prepares the silicon chip with the variation of uniform continuous pattern using photoetching and deep silicon etching technology.
The photoetching is that the figure on photolithography plate is carried out 1:1 is precisely transferred on silicon chip.In order to ensure the silicon of silicon column array structure
Silicon column length is 10~50 microns in piece, and the depth of deep silicon etching is 10~50 microns in deep silicon etching processing.
The silver nitrate aqueous solution and 3~5g/L aqueous citric acid solutions of 1~3g/L is 1 according to volume ratio：1 ratio mixes
Uniformly, electrodeposit liquid is obtained.According to a preferred embodiment of the invention, the electrodeposit liquid be 2g/L silver nitrate aqueous solution and
4g/L aqueous citric acid solutions are 1 according to volume ratio：1 ratio mixes uniformly.The volume of electrodeposit liquid is in electrodeposit reaction
10~60 milliliters.
Compared with prior art, the present invention having advantageous effect below：
1, method of the invention utilizes photoetching process combination deep silicon etching technology, and receiving for certain arrangement mode is etched on silicon chip
Rice silicon column array prepares Au nanometers of seeds, simple electricity using silicon column array as template by the non-solvent magnetron sputtering method of physics
Chemical deposition assemble nanometer silver silicon column array chip.Nano silver silicon column array prepared by this method has super-hydrophobic effect, should
The contact angle of surface and water is more than 140 degree.The super-hydrophobic effect plays the role of enrichment method to determinand.I.e. with aqueous solvent
Evaporation, solute molecule has stayed in chip surface, and is slowly enriched with, and the region of a very little is concentrated to, and ultimately forms super dense
One point of contracting.Sample acquisition is carried out to enrichment method point using raman microspectroscopy spectrum, in the SERS enhancings and concentration of the chip
Under the double action of enrichment, overdelicate detection signal can get.
2, when nano material prepared by traditional handicraft is used for detection molecules as SERS substrates, determinand is often with solution shape
State exists, and solution is needed to its volume, concentration, and quantity of solvent is precisely determined.It is then soaked in again with SERS substrates to be measured molten
In liquid, entire pretreatment process at least needs 30min, and solvent is also required to several milliliters to hundreds of milliliters and differs, time-consuming and laborious.And it is somebody's turn to do
The low-concentration liquid of chip detection, volume only need 3-5 microlitres, and pretreatment time is only the time of this 3-5 microlitres of water volatilization,
That is 5-10 minutes or so, can effective solution at present to low concentration substance detect there are the problem of, be a kind of hypersensitive, it is fast to ring
It answers, the test method of low solvent loss rate has good actual application value.
3, the present invention is prepared in nano silver silicon column array surface enhancing Raman scattering substrate, the nano silver silicon column of vertical growth
Array has three-dimensional hierarchical structure, can generate stronger needle point effect, and uniform nano array structure can be generated effectively
Ion resonance, silver nanoparticle stability is good, has the effect of collaboration enhancing, can get highly sensitive SERS effects.Meanwhile passing through knot
Condensation concentration effect is closed, testing molecule can be preferably enriched with, it is made to navigate to the region that can generate strong local electric field, to
Obtain overdelicate detectivity.
Description of the drawings
Fig. 1 is the SEM figures of the silicon chip of the equal one array architecture pattern of 2 microns × 2 microns of 1 medium spacing of embodiment；
Fig. 2 is the uniform silicon column array junctions that etching depth is 30 microns, silicon column spacing is 2 microns × 2 microns in embodiment 1
The SEM of the silicon chip of structure schemes；
Fig. 3 is the SEM figures of the chip of nano silver silicon column array structure in embodiment 1；
Fig. 4 is that molecule enrichment super-hydrophobic in embodiment 1 concentrates chip surface and water contact angle test chart；
Fig. 5 is that molecule enrichment concentration chip super-hydrophobic in embodiment 1 detects figure to the hypersensitive of R6G；
Fig. 6 is that molecule enrichment concentration chip super-hydrophobic in embodiment 1 detects figure to the hypersensitive of NTO；
Fig. 7 is the SEM figures of the silicon chip of the equal one array architecture pattern of 4 microns × 4 microns of 2 medium spacing of embodiment；
Fig. 8 is the uniform silicon column array junctions that etching depth is 10 microns, silicon column spacing is 4 microns × 4 microns in embodiment 2
The SEM of the silicon chip of structure schemes；
Fig. 9 is the SEM figures of the chip of nano silver silicon column array structure in embodiment 2；
Figure 10 is that molecule enrichment super-hydrophobic in embodiment 2 concentrates chip surface and water contact angle test chart；
Figure 11 is that molecule enrichment concentration chip super-hydrophobic in embodiment 2 detects figure to the hypersensitive of R6G；
Figure 12 is the SEM figures of the silicon chip of the equal one array architecture pattern of 2 microns × 2 microns of 3 medium spacing of embodiment；
Figure 13 is the uniform silicon column array that etching depth is 10 microns, silicon column spacing is 2 microns × 2 microns in embodiment 3
The SEM of the silicon chip of structure schemes；
Figure 14 is the SEM figures of the chip of nano silver silicon column array structure in embodiment 3；
Figure 15 is that molecule enrichment super-hydrophobic in embodiment 3 concentrates chip surface and water contact angle test chart；
Figure 16 is that molecule enrichment concentration chip super-hydrophobic in embodiment 3 detects figure to the hypersensitive of R6G.
Specific implementation mode
With reference to the embodiment of the present invention, the invention will be further elaborated.
Embodiment 1：
Step 1：The preparation of template
The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, is then toasted；
The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, place is exposed after the completion of contraposition
Reason, then carries out development treatment, obtains the silicon chip (figure for the equal one array architecture pattern that pattern is 2 microns × 2 microns of spacing
1) deep silicon etching processing then, is carried out to silicon chip, deep silicon etching depth is 30 microns, and it is 30 microns, silicon to have obtained etching depth
The silicon chip (Fig. 2) for the uniform silicon column array structure that intercolumniation is 2 microns × 2 microns, then sprayed crystal film Au by magnetron sputtering
It penetrates on the silicon chip of silicon column array structure and obtains mould material, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is
90s；
Step 2: the preparation of super-hydrophobic molecule enrichment concentration chip
The silver nitrate aqueous solution and 4g/L aqueous citric acid solutions of 2g/L is 1 according to volume ratio：1 ratio mixes uniformly,
Obtain electrodeposit liquid；Using the graphite cleaned up as cathode, mould material is placed in the electrodeposit liquid and uses as anode
The current response of 200~800mA obtains the chip (Fig. 3) with nano silver silicon column array structure for 2~6 hours, with clear after taking-up
Water cleans up, then is dried up with pure argon, obtains the super-hydrophobic molecule enrichment concentration chip.
Step 3：Application of the super-hydrophobic molecule enrichment concentration chip in SERS
It is with plasma cleaning instrument that the citric acid cleaning for remaining in nano silver silicon column array surface is clean, to eliminate citric acid
Interference of the Raman signal to testing molecule.The ultra-hydrophobicity (Fig. 4) that the substrate is verified with contact angle instrument, can obtain its surface with
The contact angle of water is 154 degree, belongs to the surface of superhydrophobic property.
The nano silver silicon column array chip cleaned up is kept flat on the table, 3-5 microlitres of testing liquid rhodamine 6G is taken
(R6G) chip surface is dropped in, after standing 5-8 minutes, the trace left after observation drop evaporation, with confocal laser Raman spectrum
Instrument is focused acquisition to drop enrichment concentrated area, carries out SERS detections (Fig. 5).
Step 4：Super-hydrophobic molecule enrichment concentration chip detects the hypersensitive of water-insoluble explosive
When carrying out trace detection to explosive NTO not soluble in water, it is contemplated that such molecule has protonated hydrogen, therefore
By alkalization, so that it is reacted with NaOH, carried out hydrophily synthesis.Become soluble-salt.The hydrophily synthetic method is suitable
For all indissoluble water substances with this feature.
The nano silver silicon column array chip cleaned up is kept flat on the table, 3-5 microlitres of testing liquid explosive NTO is taken
Chip surface is dropped in, after standing 5-8 minutes, the trace left after observation drop evaporation, with confocal laser Raman spectrometer pair
Drop enrichment concentrated area is focused acquisition, carries out SERS detections (Fig. 6).
Embodiment 2：
Step 1：The preparation of template
The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, is then toasted；
The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, place is exposed after the completion of contraposition
Reason, then carries out development treatment, obtains the silicon chip (figure for the equal one array architecture pattern that pattern is 4 microns × 4 microns of spacing
7) deep silicon etching processing then, is carried out to silicon chip, deep silicon etching depth is 30 microns, and it is 10 microns, silicon to have obtained etching depth
The silicon chip (Fig. 8) for the uniform silicon column array structure that intercolumniation is 4 microns × 4 microns, then sprayed crystal film Au by magnetron sputtering
It penetrates on the silicon chip of silicon column array structure and obtains mould material, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is
90s；
Step 2: the preparation of super-hydrophobic molecule enrichment concentration chip
The silver nitrate aqueous solution and 4g/L aqueous citric acid solutions of 2g/L is 1 according to volume ratio：1 ratio mixes uniformly,
Obtain electrodeposit liquid；Using the graphite cleaned up as cathode, mould material is placed in the electrodeposit liquid and uses as anode
The current response of 200~800mA obtains the chip (Fig. 9) with nano silver silicon column array structure for 2~6 hours, with clear after taking-up
Water cleans up, then is dried up with pure argon, obtains the super-hydrophobic molecule enrichment concentration chip.
Step 3：Application of the super-hydrophobic molecule enrichment concentration chip in SERS
It is with plasma cleaning instrument that the citric acid cleaning for remaining in nano silver silicon column array surface is clean, to eliminate citric acid
Interference of the Raman signal to testing molecule.The ultra-hydrophobicity (Figure 10) that the substrate is verified with contact angle instrument, can obtain its surface
Contact angle with water is 140 degree, belongs to the surface of superhydrophobic property.
The nano silver silicon column array chip cleaned up is kept flat on the table, 3-5 microlitres of testing liquid rhodamine 6G is taken
(R6G) chip surface is dropped in, after standing 5-8 minutes, the trace left after observation drop evaporation, with confocal laser Raman spectrum
Instrument is focused acquisition to drop enrichment concentrated area, carries out SERS detections (Figure 11).
Embodiment 3：
Step 1：The preparation of template
The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, is then toasted；
The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, place is exposed after the completion of contraposition
Reason, then carries out development treatment, obtains the silicon chip (figure for the equal one array architecture pattern that pattern is 2 microns × 2 microns of spacing
12) deep silicon etching processing then, is carried out to silicon chip, deep silicon etching depth is 30 microns, and it is 10 microns, silicon to have obtained etching depth
The silicon chip (Figure 13) for the uniform silicon column array structure that intercolumniation is 2 microns × 2 microns, then sprayed crystal film Au by magnetron sputtering
It penetrates on the silicon chip of silicon column array structure and obtains mould material, the electric current of magnetron sputtering is 30mA, and the time of magnetron sputtering is
90s；
Step 2: the preparation of super-hydrophobic molecule enrichment concentration chip
The silver nitrate aqueous solution and 4g/L aqueous citric acid solutions of 2g/L is 1 according to volume ratio：1 ratio mixes uniformly,
Obtain electrodeposit liquid；Using the graphite cleaned up as cathode, mould material is placed in the electrodeposit liquid and uses as anode
The current response of 200~800mA obtains the chip (Figure 14) with nano silver silicon column array structure for 2~6 hours, with clear after taking-up
Water cleans up, then is dried up with pure argon, obtains the super-hydrophobic molecule enrichment concentration chip.
Step 3：The SERS applications of super-hydrophobic molecule enrichment concentration chip
It is with plasma cleaning instrument that the citric acid cleaning for remaining in nano silver silicon column array surface is clean, to eliminate citric acid
Interference of the Raman signal to testing molecule.The ultra-hydrophobicity (Figure 15) that the substrate is verified with contact angle instrument, can obtain its surface
Contact angle with water is 150 degree, belongs to the surface of superhydrophobic property.
The nano silver silicon column array chip cleaned up is kept flat on the table, 3-5 microlitres of testing liquid rhodamine 6G is taken
(R6G) chip surface is dropped in, after standing 5-8 minutes, the trace left after observation drop evaporation, with confocal laser Raman spectrum
Instrument is focused acquisition to drop enrichment concentrated area, carries out SERS detections (Figure 16).
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair
Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that people in the art
Member can be designed that a lot of other modification and implementations, these modifications and implementations will be fallen in principle disclosed in the present application
Within scope and spirit.
Claims (5)
1. a kind of super-hydrophobic molecule enrichment concentration chip, it is characterised in that the super-hydrophobic molecule enrichment concentrates chip and is
Square or the nano silver silicon column of hexagon uniform array lattice structure arrangement, the nano silver silicon column are uniformly to be wrapped in silicon column
Wrap up in nano silver, the lamellar structure that nano silver is 1~2 micron, nano silver silicon column is 12~55 microns of height, 2~5 microns a diameter of
Regular column, the gap between nano silver silicon column is 8~12nm；The described super-hydrophobic molecule enrichment concentration chip use with
Lower preparation method is made：
Step A：The silicon chip cleaned up is subjected to tackified finish, and by photoresist uniform gluing to silicon chip, is then dried
It is roasting；The pattern on the silicon chip and photolithography plate after baking is subjected to contraposition in advance again and automatic aligning operates, is exposed after the completion of contraposition
Then light processing carries out development treatment, obtain the silicon chip of equal one array architecture pattern, is then carried out at deep silicon etching to silicon chip
Reason, obtains the silicon chip of uniform silicon column array structure, then crystal film Au is injected in the silicon of silicon column array structure by magnetron sputtering
On piece obtains mould material；
Step B：The silver nitrate aqueous solution and 3~5g/L aqueous citric acid solutions of 1~3g/L is 1 according to volume ratio：1 ratio is mutually mixed
It closes uniformly, obtains electrodeposit liquid；Using the graphite cleaned up as cathode, it is heavy to be placed in the electricity as anode for mould material
Electrodeposit reaction obtains the chip with nano silver silicon column array structure in hydrops, is cleaned up with clear water after taking-up, then with pure
Argon gas dries up, and obtains the super-hydrophobic molecule enrichment concentration chip.
2. super-hydrophobic molecule enrichment concentration chip according to claim 1, it is characterised in that super-hydrophobic point
Son enrichment concentration chip has super-hydrophobic effect, contact angle >=140 ° with water.
3. super-hydrophobic molecule enrichment concentration chip as claimed in claim 1 or 2 is in the application of SERS, it is characterised in that including with
Lower step：It is with plasma cleaning instrument that the citric acid cleaning for remaining in super-hydrophobic molecule enrichment concentration chip surface is clean, so
The super-hydrophobic molecule enrichment concentration chip cleaned up is put on the table afterwards, 3~5 microlitres of testing liquids is taken to drop in chip list
Face stands 5~8 minutes, and the trace left after observation drop evaporation is enriched with drop with confocal laser Raman spectrometer and concentrates
Region is focused acquisition, carries out SERS detections.
4. super-hydrophobic molecule enrichment concentration chip according to claim 3 is in the application of SERS, it is characterised in that be measured
Liquid is the one kind being dissolved in water or explosive not soluble in water, organic pollution, organic dyestuff, drug molecule.
5. super-hydrophobic molecule enrichment concentration chip according to claim 3 is in the application of SERS, it is characterised in that work as institute
When the testing liquid stated is liquid not soluble in water, being acidified or being alkalized to testing liquid becomes soluble-salt and carries out again
Detection.
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| CN108895690B (en) * | 2018-07-05 | 2019-06-25 | 南京大学 | A kind of silicon-based semiconductor-metal nanometer composite material and preparation method thereof |
| CN109975270B (en) * | 2019-04-12 | 2020-10-16 | 北京师范大学 | Silver nanoflower periodic array SERS substrate and preparation method thereof |
| CN110170747B (en) * | 2019-06-24 | 2021-05-04 | 吉林大学 | Preparation method of bionic coupling water-collecting aluminum alloy anti-icing surface |
| CN113620236A (en) * | 2020-05-06 | 2021-11-09 | 中国科学院微电子研究所 | Array preparation method of organic semiconductor material |
| CN112744783B (en) * | 2021-01-06 | 2024-04-09 | 南京大学 | Preparation method of super-hydrophobic and super-oleophobic surface with micro-nano composite structure |
| CN114324290B (en) * | 2021-12-27 | 2023-07-25 | 山东大学 | Preparation method of bionic-based super-hydrophobic integrated chip, SERS platform and application |
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