CN101475173A - Method for preparing super-hydrophobic antireflex micron and nano composite structure surface - Google Patents
Method for preparing super-hydrophobic antireflex micron and nano composite structure surface Download PDFInfo
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Abstract
The invention belongs to the technical field of preparing the surface of a composite structure, and in particular relates to a method for preparing super-hydrophobic antireflective silicon surface with a micron and nanometer composite structure. The method comprises the following steps: cleaning a silicon chip; preparing a micron-level silicon island and a gridding structure on the surface of the silicon chip; carrying out catalytic etching taking silver or aurum nanoparticles as blockage; obtaining the surface of the micron and nanometer composite structure; and carrying out chemical modification of the surface of the composite structure. A static contact angle between the super-hydrophobic antireflective material surface prepared by the method and water is more than 150 degrees, and a static rolling angle of water is less than 3 degrees. The surface has superior antireflective performance, and in particular, the light reflectivity within the wavelength range between 800 and 1,100 nm is less than 3 percent. With application of the method, the super-hydrophobic antireflective silicon surface of the micron and nanometer composite structure can be produced on scale, can be widely applied to a solar cell, a microfluidic chip, a photoelectric device, and the like, and has good industrial application prospect.
Description
Technical field
The invention belongs to the preparing technical field of composite structure surface, be specifically related to the preparation method of the super-hydrophobic antireflex silicon face of a kind of micron and nano composite structure.
Background technology
Countries in the world have given great enthusiasm and concern to little electric system (MEMS) in recent years, and it is just becoming the large-scale industry of new emergence, becomes the national economy new growth point, and the development of science and techniques of defence is produced great effect.But along with the microminiaturization of device and system, its characteristic dimension reduces, surface-area (L
2) and volume (L
3) ratio also increase relatively, surface effects strengthens, the surface force that has been left in the basket in macro-scale plays a leading role now, produces a series of problems such as surface friction, wearing and tearing, adhesion and the pressure-losses thus, makes that (MEMS) device has been subjected to great puzzlement.
Super hydrophobic surface generally is meant and the contact angle of the water surface greater than 150 °.It has special infiltration character, have waterproof, antifog, anti-cleaning, important feature such as anti-oxidant, have wide practical use at numerous areas such as scientific research and production, lives, for example can be applicable to eyeglass, optics, textiles, engineering goods, pipeline transportation, micro-fluid chip etc.This class special property can reduce the adhesive power and the frictional force of device surface, improves the flowing property of liquid in microfluidic device.The Japan mechanical engineering laboratory YasuhisaAndo of University of tsukuba is published in Sensors and Actuators, Vol.57No.2 (1996), p, the V.Studer of 83～89 paper and France is published in AppI.Phys.Lett.80, and the trial Journal of Sex Research has been carried out in the application to super hydrophobic surface in 3614 (2002) the paper.The method of solid material surface being carried out super-hydrophobic modification mainly contains two kinds: a kind of is to construct coarse micro nano structure at contact angle greater than 90 ° hydrophobic surface; Another kind is at the material of finishing low surface energy, is published in Adv.Mater.2002 as Jiang Lei, and is illustrated in 14:1857～180.Solid hydrophobic surface modification in conjunction with above-mentioned two kinds of methods has also had some reports.For example (Chinese patent, publication number CN1378581A, CN1613565A, CN1624062A), Langmuir2008,24,10421～10426.But the method general technology more complicated on some above-mentioned constructing super-drainage surfaces, and need special instrument and equipment, be difficult to realize large-area preparation.Therefore, the super-hydrophobic technology of preparing of exploring new cheapness has prior value.
Because the common plane substrate has very high reflectivity, causing optical system to be subjected to veiling glare disturbs, seriously influence the transmitance and the image analysis ability of optical element in the optical system, cause the resolving power and the sensitivity of optical system to descend, seriously influenced the performance of optics and optoelectronics device, for example solar cell, indicating meter, optical pickocff, polaroid, optical frames are first-class.In order to improve the performance of these devices, need to reduce substrate surface to the reflection of light rate.The method of tradition constructing anti-reflection sub-wavelength surface tissue mainly contains: electron beam lithography, based on the etching at dried quarter of nano impression, laser interference etching etc.For the constructing anti-reflection surface, the scientific worker has carried out number of research projects, and wherein with strongest influence power is method (Opt.Lett.1999,24,1422 of electron beam lithography; Microeletron.Eng.2005,78～79,287).Though the method for electron beam lithography has advantages such as high precision, high resolving power, because instrument costliness, shortcoming that efficient is lower have restricted it and used widely.Based on the mask of structure, laser interference etching and the nano impression of the preparation of the method for self-assembled nanometer particle, RIE can construct out sub-wavelength structure (the Nanotechnology 2000.11.161 with antireflective property on big area; Nanotechnology 1997.8.53; AppI.Phys.Lett.2002.80.2242; J.Vac.Sci.Tehchnol.2003.21.287 4Small 2008.4.1972 Chinese patent, publication number CN1378581A, CN1613565 A, CN1624062 A), yet the instrument of these Technology Needs is still very expensive, makes its application seriously limited.
Summary of the invention
The objective of the invention is to prepare large-area super-hydrophobic antireflex silicon face with a kind of simple method, proposition be a kind of preparation method with micron and super-hydrophobic antireflex silicon face of nano composite structure.The present invention utilizes anisotropic etching effect and the silver-colored catalysis etch silicon method of silicon single crystal in basic solution to prepare the composite structure that surface microstructure is micron and the common existence of nanostructure, by containing the fluoro silylating reagent chemically modified is carried out on its surface again, the silicon face of preparation has good super-hydrophobic and antireflective property simultaneously.The static contact angle that uses the surface of super-hydrophobic antireflex material of this method preparation and water is greater than 150 °, as Fig. 7 water droplet at this lip-deep slide angle less than 3 ° (static contact angle and roll angle are all tested on contact angle OCA20.DATAPHYSICS).This surface also has good antireflective property, especially in 800～1100nm wavelength region luminous reflectance factor less than 3%.
That method of the present invention has is simple to operate, universality good, with low cost, big area, rapidly and efficiently wait advantage; provide a kind of new preparation approach for expanding the application of silicon materials in industrial production; the super-hydrophobic antireflex silicon face of micro-nano compound structure is produced on a large scale; can be widely used in aspects such as solar cell, micro-fluid chip, photoelectric device, have favorable industrial application prospect.
In order to realize preparing super-hydrophobic antireflex micron nano composite structure silicon face, the scheme that the present invention adopts is in silicon face constructing micrometre successively and nanostructure, wherein the height of micron order silicon island or grid (photoetching method obtains being grid structure) is 1～7 μ m, and the diameter of nano aperture is about 80～140nm.
The method of the super-hydrophobic antireflex silicon face of preparation micron of the present invention and nano composite structure comprises the steps:
(1) chooses the silicon chip of crystal formations such as n-100, p-100, n-111, p-111, and its surface carried out clean, the process of handling is: silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water, ultrasonic power is 50～150W, time 1～10min puts into silicon chip massfraction and is 5～10min in 1～10% the HF solution then, removes the silicon-dioxide on surface, use washed with de-ionized water at last, dry up with high pure nitrogen then;
(2) by the method for alkaline solution etching, RIE etching, photoetching or nano impression, form micron order silicon island or grid on the surface of silicon chip;
The method of the alkaline solution etching described in the aforesaid method, be that the silicon chip after the cleaning is put into pH is 10～14 40 ℃～110 ℃ KOH, NaOH, EDP (mixing solutions of quadrol, pyrocatechol and water) and ammonia soln 0.5～3h, because basic solution is to the anisotropic etching effect of silicon, thereby prepared the micron order silicon island at silicon face, the height of silicon island is 5～7 μ m;
The method of the RIE etching described in the aforesaid method is on the silicon face after the array of PS ball that tight six sides of individual layer on the water surface are piled up is transferred to cleaning, then the sample that obtains is prepared the silicon island microstructure by the RIE etching, and the gas of etching is SF
6(20～45sccm) and CHF
3(3～12sccm), the power 80～160W of etching, chamber pressure 25～60mTorr, etching time 300～1000s, the micron order silicon island that obtains, its stereoscan photograph as shown in Figure 4, the height of silicon island is 1.0～3.0 μ m.
The method of the photoetching described in the aforesaid method is to select for use silicon chip after the cleaning as base material, through oxygen plasma system handles 2～8min, makes cleaning surfaces and hydrophilic before using, and is convenient to the spin-coating film of photoresist material.The condition of spin coating photoresist material is: 1000～2500 commentaries on classics/S, and rotation 15～60S, 25～45min quenches sample after spin coating finishes under 80～100 ℃ of conditions.Under the mask exposure machine, control exposure electric current 3.5A then, exposure 40s, the development 1-3s in developing solution (BP～212 ultraviolet eurymeric photoresist developing liquid) that finishes exposes, put into distilled water and clean residual developing solution, dry up with nitrogen, promptly get photoresist material micron grid structure, microstructure cycles 10 μ m, hole 5 μ m, strip width 5 μ m.Then the sample that obtains is prepared the micron silicon grid structure by the RIE etching, the gas of etching is SF
6(20～45sccm) and CHF
3(3～12sccm), the power 80～160W of etching, chamber pressure 25～60mTorr, etching time 600～1500s, the height of the micron silicon grid of preparation are 3～6 μ m.
The method of the nano impression described in the aforesaid method, it is thermoplastics type's high molecular polymer MRI～7030 (the Micro Resist company that takes a morsel, Germany) or polymetylmethacrylate be spun on the silicon chip surface after the cleaning, spin coating thickness is about 200～500nm, utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the template of silicon nitride material, the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m) construct out polymer and formwork structure complementary ordered structure, the method for promptly utilizing nano impression is at substrate surface constructing micrometre level structure.Utilizing oxygen plasma to remove interlattice polymer layer then, expose silicon chip surface, is that the blocking layer prepares the micron order silicon island by the RIE etching with the sample that obtains with the polymkeric substance of lattice structure then, and the gas of etching is SF
6(20～45sccm) and CHF
3(3～12sccm), the power 80～160W of etching, chamber pressure 25～60mTorr, etching time 500～1500s, the height of the silicon island that obtains are 2～4.5 μ m.
(3) method by electroless deposition, galvanic deposit or chemical vapour deposition is deposited on the surface of micron order silicon island or grid structure with gold or silver-colored nanoparticle, and the thickness of sedimentary gold or Nano silver grain is 5～15nm; Then the silicon chip on micron order silicon island or grid structure surface is put into HF/H
2O
2/ H
2(massfraction is that 40～60% HF, massfraction are 20～40% H in the O solution
2O
2, H
2The volume ratio of O is 1～3:5～8:10～15, carries out the catalysis etching, and then preparation nano level hole, at last with massfraction be nitric acid dousing 5～10min of 30～50% with silver or golden nanometer particle flush away, and then obtain the surface of multiple meter and nano composite structure;
The method of the electroless deposition described in the aforesaid method, be with surface preparation the silicon chip of micron order silicon island or grid put into HF and the 0.01～0.02MAgNO of 4～5M
3Mixing solutions in, electroless deposition Nano silver grain, depositing time are 1～4min;
The method of the galvanic deposit described in the aforesaid method, be with surface preparation the silicon chip of micron order silicon island or grid put into the electrolytic solution AgNO of 0.01～0.05M
3In, deposition voltage is 400～800mv, depositing time is 10～20min; Or with surface preparation the silicon chip of micron order silicon island or grid put in the electrolytic solution hydrochloro-auric acid of 0.01～0.05M, deposition voltage is 500～700mv, depositing time is 8～20min;
(4) chemically modified is carried out on the micron and the surface of nanoscale structures that have prepared: will obtain micron and the silicon chip of nano composite structure surface put into clean glass culture dish, drip 0.5～1.0ml fluoro silylating reagent in the culture dish bottom, as 17 fluorine decyl Trimethoxy silanes, Perfluorooctane sulfonates (PFOS), perfluor decyl triethoxyl silane (PFDTES), dodecyl trichlorosilane (DTS), octadecyl trichlorosilane (ODTS), perfluoro capryl dimethyl dichlorosilane (DMCS) (TFPS) etc., be heated to 100～350 ℃ and keep 1～3.5h, cool to room temperature then so just obtains having the super-hydrophobic antireflex silicon face of micron and nano composite structure.
The super-hydrophobic antireflex silicon face of the micron/nano composite structure that the present invention is prepared has many advantages and favorable application.
(1) present method technology is simple, cheap, and universality is very strong, is easy to produce;
(2) the present invention need not any template, can realize large-area preparation, referring to Fig. 9.
(3) micron/nano composite structure surface of the present invention has very large contact angle (greater than 150 °), and very little contact angle hysteresis (less than 3 °), the dust realization automatically cleaning that the globule rolls in the above and can take away the surface;
(4) super hydrophobic surface cannot not have stickingly water, and self-cleaning function can be used for some drag reduction original papers of microelectronics micro mechanical system, to reduce noise and to reduce friction and prevent corrosion;
(5) low surface energy and superhydrophobic characteristic can reduce microchannel and lose along stroke pressure, increases the fluidic velocity of flow, can be used for the conveying of the free of losses ultramicron liquid in the micro-fluid chip;
(6) silicon face of micron/nano composite structure can be widely used in aspects such as solar cell, photoelectric device with antireflecting performance.
Description of drawings
Fig. 1: the process schematic representation of preparation micron and nano composite structure super-hydrophobic antireflex silicon face;
Fig. 2: the SEM picture of the silicon island structure of preparation;
Fig. 3: monolayer alignment is the SEM picture of the PS ball of 1.1 μ m at the diameter of silicon chip surface;
Fig. 4: with diameter is that the PS ball of 1.1 μ m is done shelves layer, the SEM picture of the silicon island that the RIE etch silicon obtains;
Fig. 5: the SEM picture behind the electroless deposition Nano silver grain of surface, silicon island;
Fig. 6: the SEM picture of the micron and nanometer composite structure of preparation;
Fig. 7: the CCD photo of measuring contact angle;
Fig. 8: reflection spectrum curve;
Fig. 9: the digital camera photo (right side) of the super-hydrophobic antireflex silicon face of prepared big area micron/nano composite structure and the contrast photo (left side) of corresponding silicon chip.
As shown in Figure 1, at first choose n-100 type silicon chip, and cleaning is carried out on its surface. Then will It puts into pH is 14,60 ℃, KOH solution 1h, obtains the micron silicon island structure of silicon face. Exist then Surface deposition gold or the Nano silver grain of silicon island structure. At last, by gold or silver-colored catalysis etching preparation micron and The composite construction of nanometer.
As shown in Figure 2, be the silicon island structure of preparation, the base length of side of silicon island is 4～6 μ m, highly is 5～7 μ m. Concrete preparation process is referring to embodiment 1
As shown in Figure 3, individual layer PS ball on the water surface is transferred on the silicon face, examined with SEM Survey the array of PS ball, can find out that from SEM figure we prepare the PS ball of tight Hexagonal packing Array structure. Detailed process is referring to embodiment 6.
As shown in Figure 4, be that the PS ball monolayer alignment of 1.1 μ m prepares the silicon island micro-structural at the sample of silicon chip surface by the RIE etching with the diameter that obtains, the gas of etching is SF6(30sccm) and CHF3(6
sccm)(SF
6：CHF
3=5:1), the power 100W of etching, chamber pressure 30mTorr, etch period Be 710s. Detailed process is referring to embodiment 6.
As shown in Figure 5, on the deposition of the surface uniform of silicon island the nano particle of layer of metal silver, nanoparticle The particle diameter of son is about 100nm, and therefore, the size of the resulting nano aperture of next step catalysis etching also is About 100nm. Shown two silicon island in the picture, the lower right corner is the island nose part of one of them silicon island, after Face be a side of silicon island, deposited uniformly one deck nano particle above can finding out. The detailed process ginseng See embodiment 1.
As shown in Figure 6, be micron and the nano composite structure of preparation, we can find out afterwards micron island of etching Structure remain intact, and prepare nano aperture structure about 100nm by the surface that is etched in the island, Realized micro-nano compound structure. Detailed process is referring to embodiment 1.
As shown in Figure 7, in the CCD photo of contact angle, the edge contour of water droplet is not very clear, and reason is Because the roll angle of preparation structure is very little, water droplet is rolling, this illustrate also that we prepare structure have well Super-hydrophobic effect. Detailed process is referring to embodiment 1.
As shown in Figure 8, be the reflectance spectrum curve, curve a is directly heavy at the silicon chip surface of no silicon island structure Long-pending Nano silver grain, the reflectance spectrum curve of the nanoscale structures that then catalysis etching obtains. Curve b is us The reflectance spectrum curve of the micron and nanometer composite structure of preparation has well anti-in the whole wave-length coverage of measuring Reflecting effect, especially in 800～1100nm wavelength, its reflectivity is lower than 3%. Curve c is the pure silicon sheet The reflectance spectrum curve, its reflectivity is 40%. Curve d is the reflectance spectrum curve of silicon island structure. Specifically Process is referring to embodiment 1.
As shown in Figure 9, be the digital camera photo of the micron and nanometer composite structure for preparing at whole silicon chip, from shining Can find out on our structure not have big defective on the sheet, be fit to large tracts of land processing.
Embodiment
Embodiment 1:
(1) chooses n-100 type silicon chip, and clean is carried out on its surface.The process of handling is: silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water, ultrasonic power is 100W, time 5min.Then silicon chip is put into massfraction and be 5min in 1% the HF solution, remove the silicon-dioxide on surface, use washed with de-ionized water at last, high pure nitrogen dries up.
(2) prepare the micron silicon island structure at silicon face, process is as follows: it is 14 60 ℃ KOH solution 1h that the silicon chip that will carry out clean is put into pH, silicon is by anisotropic etching in basic solution, thereby the silicon island structure that has prepared silicon face, the base length of side of silicon island is 4～6 μ m, highly is 5～7 μ m.As shown in Figure 2.
(3) at the surface preparation nano level hole of micron order silicon island, at first with surface preparation the silicon chip of silicon island put into the HF of 4.6M and the AgNO of 0.01M
3Mixing solutions in, electroless deposition Nano silver grain 1 minute, as shown in Figure 5.Then surface length there is the silicon island structure of Nano silver grain to put into HF/H
2O
2/ H
2(49%HF that massfraction is, massfraction are 30% H in the mixing solutions of O
2O
2, and H
2The volume ratio of O is 1:5:10), carry out catalysis etching 30s, with preparation nano level hole.Be that 30% nitric acid dousing 5min is with the Nano silver grain flush away, as shown in Figure 6 with massfraction at last.
(4) body structure surface that has prepared is carried out chemically modified, the micron/nano composite structure that obtains is put into clean glass culture dish, drip the 17 fluorine decyl Trimethoxy silanes of 0.5ml in the culture dish bottom, be heated to 250 ℃, keep 2.5h, cool to room temperature then.The contact angle that records the surface is 156 °, as Fig. 7.Reflectivity is lower than 5%, as Fig. 8.
Embodiment 2:
Press method and the step of embodiment 1, change the electroless deposition Nano silver grain into galvanic deposit, electrolytic solution is the AgNO of 0.01M
3Solution, deposition voltage are 400mv, and depositing time is 15min, other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 1, and the silicon island height of preparation structure is 5～7 μ m, the size of nano level hole is about 130 nanometers, and contact angle is 153 °, and reflectivity is lower than 8%.
Embodiment 3:
Press method and the step of embodiment 1, change the electroless deposition Nano silver grain into the deposited Au nanoparticle, electrolytic solution is the chlorauric acid solution of 0.01M, and deposition voltage is 500mv, and depositing time is 10min, other steps are with embodiment 1, can obtain the super-hydrophobic antireflex silicon face equally, the silicon island height of preparation structure is 5～7 μ m, and the size of nano level hole is about 120 nanometers, contact angle is 150 °, and reflectivity is lower than 8%.
Embodiment 4:
Press method and the step of embodiment 1, change the electroless deposition Nano silver grain into chemical vapour deposition, the thickness of depositing silver nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 1.The silicon island height of preparation structure is 5～7 μ m, and the size of nano level hole is about 100 nanometers, and contact angle is 157 °, and reflectivity is lower than 6%.
Embodiment 5:
Press method and the step of embodiment 1, change the electroless deposition Nano silver grain into the chemical vapour deposition golden nanometer particle, the thickness of deposited gold nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 1.The silicon island height of preparation structure is 5～7 μ m, and the size of nano level hole is about 100 nanometers, and contact angle is 158 °, and reflectivity is lower than 6%.
Embodiment 6:
(1) chooses n-100 type silicon chip, and clean is carried out on its surface.The process of handling is: silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water, ultrasonic power is 100W, time 5min.Then silicon chip is put into 5min in 1% the HF solution, removed the silicon-dioxide on surface, use washed with de-ionized water at last, high pure nitrogen dries up.
(2) prepare the micron silicon island structure at silicon face, process is as follows: buying massfraction from Microparticles GmbH (Germany) is 10% PS solution, mixes with ethanol with equal-volume, and 15min is stand-by in excusing from death.At diameter is to add the 150mL high purity water in the glass culture dish of 15cm (to handle through French MILLI～Q ultrapure water instrument, resistivity is 18.2M Ω cm), getting the solution that 5 μ L prepare drips on the silicon chip, at this moment the PS microballoon scatter at the water surface and forms unordered structure, the sodium dodecyl sulfate solution that adds 5 μ L2% behind the wait 50min, at this moment the PS ball will form orderly monolayer array on the water surface, individual layer PS ball on the water surface is transferred on the silicon face, detect the array of PS ball with scanning electron microscope, as shown in Figure 3.As can be seen, we prepare the array structure of the PS ball of tight six sides accumulation from Electronic Speculum figure.Then the sample that obtains is prepared the silicon island microstructure by the RIE etching, the gas of etching is SF
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5:1), and the power 100W of etching, chamber pressure 30mTorr, etching time 380s, the scanning electron microscope picture of the silicon island microstructure that obtains is as shown in Figure 4.The silicon island height of preparation structure is 1 μ m.
(3) at micron-sized silicon island surface preparation nano level hole, at first with surface preparation the silicon chip of silicon island put into the HF of 4.6M and the AgNO of 0.01M
3Mixing solutions in, electroless deposition Nano silver grain 1min then, has the silicon island structure of Nano silver grain to put into HF/H surface length
2O
2/ H
2(massfraction is respectively 49%HF, 30%H in the O solution
2O
2And H
2The volume ratio of O is 1:5:10), carry out catalysis etching 30s, with preparation nano level hole, be that 30% nitric acid dousing 5min is with the Nano silver grain flush away with massfraction at last.
(4) structure that has prepared is carried out surface chemical modification, the micron/nano composite structure that obtains is put into clean glass culture dish, drip the 17 fluorine decyl Trimethoxy silanes of 0.5ml in the culture dish bottom, be heated to 250 ℃, keep 2.5h, cool to room temperature then.The silicon island height of preparation structure is 1 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 150 °, and reflectivity is lower than 10%.
Embodiment 7:
Press method and the step of embodiment 6, change the electroless deposition Nano silver grain into galvanic deposit, electrolytic solution is the AgNO of 0.01M
3Solution, deposition voltage are 400mv, and depositing time is 15min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 6.The silicon island height of preparation structure is 1 μ m, and the size of nano level hole is about 130 nanometers, and the contact angle size is 151 °, and reflectivity is lower than 10%.
Embodiment 8:
Press method and the step of embodiment 6, change the electroless deposition Nano silver grain into the deposited Au nanoparticle, electrolytic solution is the chlorauric acid solution of 0.01M, deposition voltage is 500mv, depositing time is 10min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 6.The silicon island height of preparation structure is 1 μ m, and the size of nano level hole is about 120 nanometers, and the contact angle size is 152 °, and reflectivity is lower than 10%.
Embodiment 9:
Press method and the step of embodiment 6, change the electroless deposition Nano silver grain into chemical vapour deposition, the thickness of depositing silver nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 6.The silicon island height of preparation structure is 1 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 154 °, and reflectivity is lower than 8%.
Embodiment 10:
Press method and the step of embodiment 6, change the electroless deposition Nano silver grain into the chemical vapour deposition golden nanometer particle, the thickness of deposited gold nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 6.The silicon island height of preparation structure is 1 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 153 °, and reflectivity is lower than 8%.
Embodiment 11:
(1) chooses n～100 type silicon chips, and clean is carried out on its surface.The process of handling is: silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water, ultrasonic power is 100W, time 5min.Then silicon chip is put into 5min in 1% the HF solution, removed the silicon-dioxide on surface, use washed with de-ionized water at last, high pure nitrogen dries up.
(2) prepare the micron silicon grid structure at silicon face, process is as follows: select for use the silicon chip that cleans above as base material, through oxygen plasma system handles 5min, made cleaning surfaces and hydrophilic before using, be convenient to the spin-coating film of photoresist material.The condition of spin coating photoresist material is: 1500 commentaries on classics/S, and rotation 15S, 30min quenches sample after spin coating finishes under 80 ℃ of conditions.Under the mask exposure machine, control exposure electric current 3.5A then, exposure 40s, the development 3s in developing solution (BP～212 ultraviolet eurymeric photoresist developing liquid) that finishes exposes, put into distilled water and clean residual developing solution, dry up with nitrogen, promptly get the photoresist material micrometer structure, microstructure cycles 10 μ m, hole 5 μ m, band 5 μ m.Then the sample that obtains is prepared silicon grid microstructure by the RIE etching, the gas of etching is SF
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5:1), and the power 100W of etching, chamber pressure 30mTorr, etching time 900s,
(3) at the surface preparation nano level hole of micron-sized silicon grid structure, at first with surface preparation the silicon chip of silicon grid put into the HF of 4.6M and the AgNO of 0.01M
3Mixing solutions in, electroless deposition Nano silver grain 1 minute then, has the silicon grid structure of Nano silver grain to put into HF/H surface length
2O
2/ H
2(49%HF, 30%H in the O solution
2O
2And H
2The volume ratio of O is 1:5:10), carry out catalysis etching 30s, with preparation nano level hole.At last with nitric acid with the Nano silver grain flush away.
(4) structure that has prepared is carried out surface chemical modification, the micron/nano composite structure that obtains is put into clean glass culture dish, drip the 17 fluorine decyl Trimethoxy silanes of 0.5ml in the culture dish bottom, be heated to 250 ℃, keep 2.5h, cool to room temperature then.The silicon grid height of preparation structure is 3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 155 °, and reflectivity is lower than 7%.
Embodiment 12:
Press method and the step of embodiment 11, change the electroless deposition Nano silver grain into galvanic deposit, electrolytic solution is the AgNO of 0.01M
3Solution, deposition voltage are 400mv, and depositing time is 15min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The height of the silicon grid structure of preparation structure is 3 μ m, and the size of nano level hole is about 130 nanometers, and the contact angle size is 153 °, and reflectivity is lower than 8%.
Embodiment 13:
Press method and the step of embodiment 11, change the electroless deposition Nano silver grain into the deposited Au nanoparticle, electrolytic solution is the chlorauric acid solution of 0.01M, deposition voltage is 500mv, depositing time is 10min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The height of the silicon grid structure of preparation structure is 3 μ m, and the size of nano level hole is about 120 nanometers, and the contact angle size is 152 °, and reflectivity is lower than 8%.
Embodiment 14:
Press method and the step of embodiment 11, change the electroless deposition Nano silver grain into chemical vapour deposition, the thickness of depositing silver nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The height of the silicon grid structure of preparation structure is 3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 156 °, and reflectivity is lower than 6%.
Embodiment 15:
Press method and the step of embodiment 11, change the electroless deposition Nano silver grain into the chemical vapour deposition golden nanometer particle, the thickness of deposited gold nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The height of the silicon grid structure of preparation structure is 3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 155 °, and reflectivity is lower than 7%.
Embodiment 16:
(1) chooses n～100 type silicon chips, and clean is carried out on its surface.The process of handling is: silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water, ultrasonic power is 100W, time 5min.Then silicon chip is put into 5min in 1% the HF solution, removed the silicon-dioxide on surface, use washed with de-ionized water at last, high pure nitrogen dries up.
(2) thermoplastics type's high molecular polymer MRI～7030 (the Micro Resist company that takes a morsel, Germany) or polymetylmethacrylate be spun on the silicon chip surface of handling well, spin coating thickness is about 200～500nm, utilize 2.5 inches nano marking press of the OBDUCAT company production of Sweden, (method by electron beam lithography is constructed with the template of silicon nitride material, the dot matrix type structure, the size dimension scope of its point is 800nm * 800nm～10 μ m * 10 μ m, the spacing dimension scope of point is 800nm～10 μ m) construct out polymer and formwork structure complementary ordered structure, the method for promptly utilizing nano impression is at substrate surface constructing micrometre level structure.Utilize oxygen plasma to remove polymer barrier layer between dot matrix then, expose silicon chip surface, then the sample that obtains is prepared the silicon island microstructure by the RIE etching, the gas of etching is SF
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5:1), the power 100W of etching, chamber pressure 30mTorr, etching time 1000s.
(3) at micron-sized silicon island surface preparation nano level hole, at first with surface preparation the silicon chip of silicon island put into HF/AgNO
3In (4.6 and 0.01M) solution, electroless deposition Nano silver grain 1 minute then, has the silicon island structure of Nano silver grain to put into HF/H surface length
2O
2/ H
2(49%HF, 30%H in the O solution
2O
2And H
2The volume ratio of O is 1:5:10), carry out catalysis etching 30s, with preparation nano level hole.At last with nitric acid with the Nano silver grain flush away.
(4) structure that has prepared is carried out surface chemical modification, the micron/nano composite structure that obtains is put into clean glass culture dish, drip the 17 fluorine decyl Trimethoxy silanes of 0.5ml in the culture dish bottom, be heated to 250 ℃, keep 2.5h, cool to room temperature then.The silicon island height of preparation structure is 2.3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 155 °, and reflectivity is lower than 6%.
Embodiment 17:
Press method and the step of embodiment 16, change the electroless deposition Nano silver grain into galvanic deposit, electrolytic solution is the AgNO of 0.01M
3Solution, deposition voltage are 400mv, and depositing time is 15min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The silicon island height of preparation structure is 2.3 μ m, and the size of nano level hole is about 130 nanometers, and the contact angle size is 152 °, and reflectivity is lower than 8%.
Embodiment 18:
Press method and the step of embodiment 16, change the electroless deposition Nano silver grain into the deposited Au nanoparticle, electrolytic solution is the chlorauric acid solution of 0.01M, deposition voltage is 500mv, depositing time is 10min, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The silicon island height of preparation structure is 2.3 μ m, and the size of nano level hole is about 120 nanometers, and the contact angle size is 150 °, and reflectivity is lower than 7%.
Embodiment 19:
Press method and the step of embodiment 16, change the electroless deposition Nano silver grain into chemical vapour deposition, the thickness of depositing silver nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The silicon island height of preparation structure is 2.3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 154 °, and reflectivity is lower than 6%.
Embodiment 20:
Press embodiment 16 methods and step, change the electroless deposition Nano silver grain into the chemical vapour deposition golden nanometer particle, the thickness of deposited gold nanoparticle is 5nm, and other steps can obtain the super-hydrophobic antireflex silicon face equally with embodiment 11.The silicon island height of preparation structure is 2.3 μ m, and the size of nano level hole is about 100 nanometers, and the contact angle size is 155 °, and reflectivity is lower than 7%.
Claims (10)
1, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure comprises the steps:
(1) chooses silicon chip, clean is carried out on its surface;
(2) by the method for alkaline solution etching, RIE etching, photoetching or nano impression, form micron order silicon island or grid structure on the surface of silicon chip;
(3) method by electroless deposition, galvanic deposit or chemical vapour deposition is deposited on the surface of micron order silicon island or grid structure with gold or silver-colored nanoparticle, and the thickness of sedimentary gold or Nano silver grain is 5～15nm; Then the silicon chip of silicon island or grid structure is put into HF/H
2O
2/ H
2In the O solution, carry out the catalysis etching, and then preparation nano level hole, at last with massfraction be nitric acid dousing 5～10min of 30～50% with silver or golden nanometer particle flush away, and then obtain micron and the surface of nano composite structure;
The micron that (4) will obtain and the silicon chip of nano composite structure surface are put into clean glass culture dish, drip 0.5～1.0ml fluoro silylating reagent in the culture dish bottom, reheat to 100～350 ℃ maintenance 1～3.5h, cool to room temperature then obtains having the super-hydrophobic antireflex silicon face of micron and nano composite structure.
2, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: it is that silicon chip is carried out ultrasonic cleaning respectively in acetone, chloroform, ethanol, water that silicon chip surface is carried out clean, ultrasonic power is 50～150W, time 1～10min, then silicon chip is put into massfraction and is 5～10min in 1～10% the HF solution, remove the silicon-dioxide on surface, use washed with de-ionized water at last, dry up with high pure nitrogen then.
3, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the method for the described alkaline solution etching of step (2), be that the silicon chip after the cleaning is put into pH is 10～14 40 ℃～100 ℃ KOH, NaOH, EDP or ammonia soln 0.5～3h, because basic solution is to the anisotropic etching effect of silicon, thereby prepared micron-sized silicon island structure at silicon face, the height of silicon island is 5～7 μ m.
4, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the method for the described RIE etching of step (2), be on the silicon face after the array of PS ball that tight six sides of individual layer on the water surface are piled up is transferred to cleaning, then the sample that obtains is prepared the silicon island microstructure by the RIE etching, the gas of etching is SF
6And CHF
3, SF
6The stream flow velocity be 20～45sccm, CHF
3Flow velocity be 3～12sccm, the power 80～160W of etching, chamber pressure 25～60mTorr, etching time 300～1000s, the height of the silicon island that obtains are 1.0～3.0 μ m.
5, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the described photoetching method of step (2), be to select for use silicon chip after the cleaning as base material, through oxygen plasma system handles 2～8min, quench behind the spin coating photoresist material, under the mask exposure machine, expose then, in developing solution, develop again, clean the back in the distilled water and dry up, promptly on silicon chip, obtain the micrometer structure of photoresist material with nitrogen; At last the silicon chip that obtains is prepared silicon grid microstructure by the RIE etching, the height of the silicon grid of preparation is 3～6 μ m.
6, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the described nano-imprinting method of step (2), be that high molecular polymer MRI～7030 or polymetylmethacrylate are spun on the silicon chip surface after the cleaning, silicon nitride with micron order dot matrix type structure is a template, constructs out high molecular polymer and the micron level ordered lattice structure of formwork structure complementary by the method for nano impression at silicon chip surface; Polymkeric substance with lattice structure is that the blocking layer prepares the micron order silicon island by the RIE etching then, and the height of the silicon island that obtains is 2～4.5 μ m.
7, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the described electroless deposition methods of step (3), be with surface preparation the silicon chip of micron order silicon island or grid structure put into HF and the 0.01～0.02M AgNO of 4～5M
3Mixing solutions in, electroless deposition Nano silver grain, depositing time are 1～4min.
8, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure, it is characterized in that: the described electro-deposition method of step (3), be with surface preparation the silicon chip of micron order silicon island or grid structure put into the electrolytic solution AgNO of 0.01～0.05M
3In, deposition voltage is 400～800mv, depositing time is 10～20min; Or with surface preparation the silicon chip of micron order silicon island or grid put in the electrolytic solution hydrochloro-auric acid of 0.01～0.05M, deposition voltage is 500～700mv, depositing time is 8～20min.
9, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: the described fluoro silylating reagent of step (4) is 17 fluorine decyl Trimethoxy silanes, Perfluorooctane sulfonates, perfluor decyl triethoxyl silane, dodecyl trichlorosilane, octadecyl trichlorosilane or perfluoro capryl dimethyl dichlorosilane (DMCS).
10, a kind of method for preparing the super-hydrophobic antireflex silicon face of micron and nano composite structure as claimed in claim 1, it is characterized in that: silicon chip is the silicon chip of n-100, p-100, n-111 or p-111 crystal formation.
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