CN101308219B - Method for constructing anti-reflection microstructure using single layer nanometer particle as etching blocking layer - Google Patents
Method for constructing anti-reflection microstructure using single layer nanometer particle as etching blocking layer Download PDFInfo
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Abstract
The invention belongs to the surface patterning microstructure construction technique, which relates to a method for constructing a microstructure with anti-reflection performance on a foundation base by combining the self-assembly technique with the reactive ion beam etching technique. The method is to take monolayer polymeric micro-spheres, silicon dioxide micro-spheres and nano-particles of metal or metal oxides as a barrier layer and implement the RIE etching to the foundation base, then an approximate cone-shaped microstructure is constructed on the foundation base, and the structure hasextreme high anti-reflection performance, thereby effectively improving the light energy utilization rate, reducing the interference of veiling glare in an optical system, increasing the optical transmittance, and further improving the sensitivity and stability of the optical system, and the method can be used for constructing large-area anti-reflection structures. The method of the invention hasadvantages of simple operation, changeable foundation base, strong applicability, good repeatability, low cost, high efficiency, adjustable anti-reflective applied wavelength and conformity to industrialized standards, and can be used for making photoelectric devices such as solar batteries and white light sensors.
Description
Technical field
The invention belongs to the patterned surface microstructure and construct technology, be specifically related to utilize self-assembling polymers microballoon, silicon dioxide microsphere or inorganic nano-particle to combine, in substrate, construct the method for microstructure with very strong antireflective property with reactive ion beam etching technique.
Background technology
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 resolution and the sensitivity of optical system to descend, seriously influenced the performance of optics and optoelectronics device, for example solar cell, display, optical sensor, 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 traditional reduction substrate surface reflectivity is to utilize the multilayer film of reflection coefficient gradient gradual change; but this multilayer film run into because the stability problem that thermal expansivity does not match or adhesive force difference etc. is brought through regular meeting; and this film is common, and only the antireflective property in the specific band scope is better, and can not be implemented in the antireflection in the broadband scope.Because the material of the low refraction coefficient of occurring in nature is less, be difficult to find the satisfactory material of refraction coefficient, so its range of application has been subjected to very big restriction.
1967, Bernhard found that first pretty young woman's eye surface is that array of protrusions by the sub-wavelength yardstick constitutes, and proposed these protruding structures and can reduce reflection of light (Endeavor 16, p.76-84,1967).The principle that scientist studies this anti-reflection structure is that protruding microstructure is equivalent to the dielectric layer that a reflection coefficient changes in gradient, therefore has reasonable antireflective property.Because this structure is made up of one matter, has overcome the antireflecting shortcoming of multilayer film, so obtain people's extensive concern.People such as Clapham have at first proposed a kind of optical exposure and the method for interfering etching to combine and have constructed the surface that the tapered array by rule covers, and all have antireflective property (U.S.P at.No.4,013,465) in than polarizers of big angle scope.Structure with antireflective property not only is confined to this well-regulated periodic structure, people such as Gombert utilize the method for interfering etching to construct out the pattern of the hawkeye structure of rule earlier, the part of utilizing methods such as mechanical friction to construct out random structure again, this two parts combination, also can effectively reduce catoptrical loss (U.S.Pat.No.6,359,735).Antireflective property is not only relevant with the shape of structure, also relevant with cycle of structure and degree of depth etc., in 2003, human metals such as Takahara are made mask, by the method formation metal lattice structure of evaporation, use RIE (reactive ion etching) etching then, in the process of etching, the metal lattice size diminishes gradually, and then forms the pyramidal structure of high length-diameter ratio, has good antireflective property (U.S.Pat.No 20030102286).
The method of tradition constructing anti-reflection sub-wavelength surface structure mainly contains: electron beam lithography, and 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 high precision, advantages such as high resolving power are because instrument costliness, shortcoming that efficient is lower have restricted it and used widely.Based on the mask of laser interference etching and nano impression, RIE can construct out sub-wavelength structure (the Nanotechnology 2000.11.161 with antireflective property on large tracts of land; Nanotechnology1997.8.53; Appl.Phys.Lett.2002.80.2242; J.Vac.Sci.Tehchnol.2003.21.2874), however the instrument of these Technology Needs is still very expensive, makes its application seriously limited.
In recent years, self-assembling technique is used to construct the sub-wavelength surface structure with antireflective property.2007, people such as Sen Wang utilized the silver-colored island that deposits on silicon base to carry out the RIE etching for mask, construct out antireflecting body structure surface (Appl.Phys.Lett.2007.91.061105).People such as Peng Jiang utilize silica spheres to be mask, obtain the orderly pattern of chromium with electron beam transpiration vapour deposition method deposition, and be that mask carries out wet etching with chromium, remove the surface with antireflective property (Appl.Phys.Lett.2007.91.231105) that can form back taper after dechromising.People such as Peng Jiang utilizes spin coating technique to form the silica nanosphere array again on silicon base subsequently, again by the substrate of RIE etch silicon, can form the surface with antireflective property (Appl.Phys.Lett.2008.92.061112) of column, but the method technology of these constructing anti-reflection structures more complicated all.
Related method is to utilize the pattern of self-assembled monolayer nano particle to be mask in this patent, by the RIE etching, constructs the array structure of taper.This construction method cost is low, substrate is adjustable, and can realize that (we prepare constructing of anti-reflection structure of the area 2cm of sample * 2cm) to large tracts of land at present, can be widely used in solar cell, white light sensing display, photoelectric device, optical mirror slip and the first-class aspect of optical frames.
Summary of the invention
The purpose of this invention is to provide a kind of structure plan of in substrate, assembling the nano particle (comprising polymer nano-microspheres, silicon dioxide nanosphere or metal nanoparticle and metal oxide nanoparticles) of individual layer by self-assembling technique, function absorption or electro-deposition method, with this pattern is the restraining barrier of RIE etching, be etched in the structure that forms taper on the surface of substrate by RIE, this structure can effectively reduce substrate to reflection of light.
The nano particle of self-assembled monolayer polymer microballoon, silicon dioxide microsphere, metal or metal oxide in substrate, and as the restraining barrier, carry out the RIE etching, so just construct the microstructure of similar taper in substrate, this structure has high antireflective property.Also can with electrodeposit metals and metal oxide or the assembled inorganic nano particle obtains as the particle of etching barrier layer.
The substrate that is fit to is silicon, glass, quartz, polymkeric substance or metal and metal oxide substrate.
Polymeric substrates is dimethyl silicone polymer (PDMS), polyurethane (PU), Polyvinylchloride (PVC), polyethylene terephthalate (PET), polystyrene (PS), tygon (PE), polypropylene (PP) or diazonium photoresist (NOA), polymethylmethacrylate (PMMA).
Metallic substrates is the metal of surfacings such as gold, silver, platinum, aluminium.
The metal oxide substrate is the metal oxide of surfacings such as alundum (Al, zinc paste, titania.
The polymer nano-microspheres that is fit to do individual layer nano particle restraining barrier is polystyrene (PS) Nano microsphere or polymethylmethacrylate (PMMA) Nano microsphere, metal (gold, silver) nano particle and metal oxide (zinc paste, titania, di-iron trioxide, manganese dioxide) nano particle etc.
Utilize the method for the constructing anti-reflection structure that this patent provides simple, substrate is variable, and antireflecting applicable wavelengths is adjustable, and good reproducibility, cost is low, efficient is high, and antireflective property is good, and applicability is strong, and the scope of application is wider.
The described method with anti-reflection structure surface of constructing of this patent may further comprise the steps:
A chooses substrate, and substrate is cleaned and hydrophilicity-imparting treatment;
B, method by self-assembling technique, function adsorption method, electro-deposition is assembled into the individual layer nano particle in the substrate, thereby in substrate, obtain the array structure of the nano particle of individual layer, the height of this array structure and cycle can be controlled by the size of control individual layer nano particle, the cycle of array structure is 100nm～10 μ m in the described method of this patent, and then can realize that the cycle of anti-reflection microstructure is 100nm～10 μ m;
C, array structure with the individual layer nano particle is the restraining barrier of RIE etching, etching is carried out in substrate, by changing condition (as: pressure of cavity, the composition of etching gas and the component of RIE etching, the time of etching and the power of etching) pattern, the degree of depth, the selection ratio of regulation and control substrate etching, thereby obtain the structure with antireflective property of taper in substrate, the reflectivity of this body structure surface is controlled in certain wavelength coverage.
Has an anti-reflection structure surface through above step is resulting, can know that by atomic force microscope, scanning electron microscope analysis we have obtained the structure of similar taper on substrate surface, and the mensuration of ultraviolet spectrum shows that the reflectivity of sample has substantial degradation.
Because the RIE etching is relevant with gas composition, the chamber pressure of etching, etching power, the etching time of etching, so we illustrate by different base materials:
A: for polymeric substrates, the gas of etching is the mixed gas of argon gas and oxygen, and its volume ratio is 0.2: 1～5: 1, and the power of etching is 30～80W, the time 200～800S of etching;
B: for silicon, quartz, substrate of glass, the gas of etching is SF
6And CHF
3, CF
4And O
2Or CF
6And O
2Mixed gas, or CF
4, the volume ratio of mixed gas is 1: 1～7: 1, and etching power is 30～100W, and etching time is 200～600S.
C: for metal and metal oxide substrate, with Ar or Ar and O
2Mixed gas, the volume ratio of mixed gas is 0.2: 1～7: 1, etching power 30～150W, etching time 300～500S.
The cleaning of silicon, glass, quartz substrate and hydrophilicity-imparting treatment:
The cleaning of substrate mainly contains two kinds of methods, and first method is at first with oxygen plasma substrate surface to be handled, and purpose is to remove the organism of remained on surface, oxygen gas flow rate 60～140mL/min, power 100～300W, processing time 5～10min; Again with high purity water to substrate surface ultrasonic cleaning 2～3 times, each time is 2～5min, makes thoroughly cleaning of surface;
Except with the said method, can also be NH in volume ratio
3H
2O: H
2O
2: H
2In the solution of O=1～3: 1～3: 3～8, soaking 30～90min under 50～90 ℃ temperature, is to clean 2～5min in 40～100W ultrasonic cleaning instrument at power then, uses the high purity water ultrasonic cleaning again 2～3 times, and each time is 2～5min;
It mainly is that massfraction is put in the substrate that above-mentioned steps is handled well is that the aqueous solution of 10～20% lauryl sodium sulfate is soaked 1～24h that hydrophilic treatment is carried out in substrate, stand-by.
The cleaning of polymeric substrates and hydrophilicity-imparting treatment:
Polymkeric substance with after 30～50W oxygen plasma treatment, 30～60s, is immersed in substrate that to soak 1～4h (hydrophilic treatment is carried out in substrate) in the aqueous solution of lauryl sodium sulfate of mass concentration 10～20% stand-by.
Metal and metal oxide substrate are handled with the method for the plasma polishing of Ar gas, and its power is 40～80W, and the polishing time is 60～120s.
It mainly is mass concentration 5～15% sodium dodecyl sulfate solutions to be put in metal and metal oxide substrate soak 1～4h that hydrophilic treatment is carried out in substrate, stand-by.
The method for preparing individual layer nano particles array structure in substrate comprises self-assembling technique, function adsorption method and electro-deposition method etc.
Self-assembling technique:
With the PS ball is the example explanation.Solution A preparation: the massfraction that will buy from Microparticles GmbH (Germany) is 10～20% PS solution and ethanol with volume ratio 0.2～5: 1 mixes, stand-by behind ultrasonic 5～10min;
It is that 5%～30% aqueous solution solution B and massfraction are that 1%～10% aqueous solution C is stand-by that lauryl sodium sulfate (enough buying in Shanghai chemical company) is mixed with massfraction.
Get volume V with microsyringe again
0The solution A of (5～25 μ L) drops on the liquid level of high purity water (handle through French MILLI～Q ultrapure water instrument, resistivity is 18.2M Ω cm) and launches, and has so just formed the unordered PS ball film of one deck on the liquid level of high purity water, placement a period of time t
1(0.5～1.5h).Along with the volatilization of PS ball solvent, PS self-organization on the liquid level of high purity water forms orderly relatively structure, but also fails to form large-area ordered individual layer because surface pressure is relatively hanged down.Get volume V afterwards
2The solution C (1%～10%) of (1～5 μ L) drips on the water surface.Because the adding of surfactant, cause the surface pressure of water to increase, spacing between the PS ball is dwindled, thereby on the water surface, form large-area ordered structure, with the substrate after cleaning and the hydrophilic treatment PS micro-sphere array of the water surface is transferred in the substrate that solution B soaked, can in substrate, obtain one the six closelypacked PS ball of side monolayer array structure, six the PS microballoons that all have on every side of each PS Nano microsphere closely link to each other in this structure, and in the middle of three adjacent microballoons a similar leg-of-mutton space are arranged.
This method is fit to various substrates recited above.
This method is fit to (as silicon dioxide microsphere, metal nanoparticle, metal oxide nanoparticles etc.) such as various polymer nano-microspheres (as PS Nano microsphere, PMMA Nano microsphere etc.) and some inorganic nano-particles.
Using self-assembling technique, to prepare the step of nano particles array structure of metal or metal oxide as follows:
With the Nano silver grain is example, get the Nano silver grain for preparing solution (Materials ResearchBulletin, 2001,36,1149-1155) 5～25mL adds the sodium citrate solution of 20mL 5%, is designated as solution D.
The monocrystalline silicon of cleaning and the clean dried crossed of hydrophilic treatment is (or quartzy, glass) the prior amino silane (aminopropyl triethoxysilane that dripped is put in substrate, hmds etc.) in etc. the vacuum dryer, being evacuated to vacuum tightness is 0.01～0.5Pa, toluene is used in taking-up successively after placing 40min～4h, chloroform, the alcohol solvent ultrasonic cleaning, each 2～15min, use the deionized water ultrasonic cleaning again 2～3 times, each 2～15min, dry up with nitrogen then, thereby in the unimolecular film of assembling silane reagent in the substrate by covalent bond, this substrate that further will prepare is again put into solution D and is soaked 20～30h.
Function absorption: will clean and the prior silane reagent that dripped is put in the monocrystalline silicon of the clean dried that hydrophilic treatment is crossed (or quartz, glass) substrate, as silicol (silanol etc.), alkyl silane (n-octyl dichlorosilane, octadecyl trichlorosilane etc.), in the vacuum dryer of amino silane (aminopropyl triethoxysilane, hmds etc.) etc., being evacuated to vacuum tightness is P
1(0.01～0.5Pa), toluene, chloroform, alcohol solvent ultrasonic cleaning are used in taking-up successively after placing 40min～4h, each 2～15min, use the deionized water ultrasonic cleaning again 2～3 times, each 2～15min, dry up with nitrogen then, thereby in the unimolecular film of assembling silane reagent in the substrate by covalent bond, afterwards substrate is soaked 10～30h and take out in the solution of the nano particle of metal or metal oxide, we have just obtained being used for the nano particle barrier layer structure shown in Fig. 8 Electronic Speculum picture of RIE etching in substrate like this.
Electro-deposition: will clean and the metal oxide of monocrystalline silicon, metallic substrates or the conduction of the clean dried that hydrophilic treatment is crossed.With the substrate is working electrode, and ITO is a contrast electrode, and deposition voltage is 400mV～900mV, electrode separation 1～3cm, and sedimentation time is 300～900s.So just can obtain the array structure of individual layer nano particle in substrate, obtain anti-reflection microstructure with the RIE etching.Electrolytic solution in the electrolytic cell is metal ion solution (as gold chloride, silver nitrate, manganese acetate, titanate esters etc.).Concentration and component by control oxidation-reduction potential and metal ion solution, can in substrate, obtain metal simple-substance or metal oxide, silver ion reduction obtains argent as with the silver nitrate electrolysis time, and divalent manganesetion is oxidized to tetravalence manganese during with the manganese acetate electrolysis, obtains metal oxide.
The synoptic diagram of the experimentation of this patent as shown in Figure 2.Since the lithographic technique of the RIE that in this patent, uses, and the selection of RIE etching is compared, shape is relevant with the gas and the material of etching.Reduce owing to do the nano particle on restraining barrier of etching or Nano microsphere himself size in the process of etching, thus be easy to etch the structure of a taper, thus significantly reduced the reflectivity of substrate surface.Here we are example with the silicon chip, use SF
6And O
2Etch silicon, when regulation and control gas with various ratio, can control etching silicon selection than and pattern, the time of the etching by control is controlled the degree of depth of etching.Along with the size on the prolongation restraining barrier of time of etching reduces gradually, be that (PS with 460nm is an example to maximum etching depth when the size on restraining barrier reaches capacity, maximum etching depth is 400nm), obtain the structure of a more satisfactory similar taper this moment, the reflectivity of the sample of this moment is minimum.
Method shown in this patent can (400～2400nm) reflectivity reduces significantly, has effectively reduced catoptrical loss, improves the efficiency of light energy utilization in certain wavelength band with substrate surface.Here with the silicon chip example, as shown in Figure 5, (reflectivity of silicon chip surface of not doing anti-reflection structure in 600～1200nm) scopes is greater than 32% at visible light and near-infrared wavelength, and by the handled material surface of the method that this patent provided, in the scope of this wavelength, can obtain reflectivity less than 5%, in wavelength 750nm～minimum its value of 930nm place reflectivity is 1.2%, effectively reduced the material surface reflectivity, and then effectively raise the efficiency of light energy utilization, reduce the interference of veiling glare in the optical system and the transmitance of raising optics, thereby improve the sensitivity and the stability of optical system.Therefore, have great practical value.And this method can be used for constructing large-area anti-reflection structure, method is simple, substrate is variable, applicability is strong, good reproducibility, cost is low, efficient is high, and antireflecting applicable wavelengths is adjustable, meets industrialized standard, can be used for photoelectric devices such as solar cell, white light sensor, reduce device cost greatly.
Description of drawings
Fig. 1: self-assembling technique prepares the process schematic representation of the PS nanosphere array structure of individual layer;
Fig. 2: the process schematic representation of constructing anti-reflection structure;
Fig. 3: the SEM picture of the array of the individual layer PS ball of self assembly;
Fig. 4: the SEM picture of anti-reflection microstructure under the best etching condition;
Fig. 5: SEM picture and spectrum under the different etching condition;
Fig. 6: the optical microscope picture that the substrate of anti-reflection microstructure is arranged;
The section S EM picture and the reflectance spectrum curve of the anti-reflection microstructure that the PS ball etching of Fig. 7: 1100nm obtains;
Fig. 8: the SEM picture of the Nano silver grain of static assembling;
Fig. 9: with the Nano silver grain is the SEM picture of mask constructing anti-reflection microstructure.
As shown in Figure 1, take silicon base and PS microballoon as example, a step is that the silicon chip that cleaning is good tilts to put into water, and the PS solution for preparing of getting certain volume drops on the silicon chip, and the PS microballoon will be in the unordered structure of water surface formation like this. B step (more clear in order to make picture, substrate is omitted and do not drawn) adds the surfactant solution of certain volume this moment again, unordered PS structure is become in order, thereby form the structure of orderly PS individual layer at the water surface; The C step is taken out the PS individual layer ball on the water surface with the good silicon chip of cleaning, and orderly PS individual layer spherical structure has just been transferred to silicon chip surface on the water surface like this.
As shown in Figure 2, the PS nano particle of self-assembled monolayer in after treatment hydrophilic substrate uses the substrate of RIE (reactive ion beam etching (RIBE)) etching to prepare the method for anti-reflection microstructure more in advance. The a step is self-assembled monolayer, compact arranged PS ball at the bottom of the hydrophilic group, the PS ball to be arranged as six sides tightly packed, six leg-of-mutton spaces are arranged, with reference to figure 3 between each ball. The b step is that the closelypacked PS ball that obtains in a step is as mask, utilize RIE (reaction particle bundle etching) etching substrate, and intercepted the gas of RIE and contacting of substrate in the place that has the PS ball to cover, so can effectively stop the etching substrate of RIE. And in the place that does not have the PS ball to cover, its etching gas can touch substrate, so fallen by the RIE selective etch. Because the RIE etching has good anisotropy (suitable gas composition and RF value) under certain conditions, along with the particle diameter of the increase PS of etch period is also diminishing gradually, the area that stops that is PS diminishes gradually, we obtain the structure of a similar taper in substrate like this, and then remove residual PS microballoon with oxolane. So, take the PS micro-sphere array as the mask etching substrate time, can obtain the structure of taper, the structure of this taper is equivalent to insert the multilayer film that reflectance factor changes step by step between substrate surface and air, effectively improves antireflective property.
As shown in Figure 3, utilize the SEM picture of the polystyrene ball array of the individual layer that self-assembling technique constructs in substrate, the scale of its scanning is 2 μ m. The SEM picture (50000 times) of the upper left corner of picture for amplifying. Can find out that from this figure the PS ball array that obtains is orderly in large tracts of land, simultaneously by can finding out that the arrangement of PS ball is closelypacked in the SEM picture that amplifies, and each ball around similar leg-of-mutton space is arranged.
As shown in Figure 4, utilize the described method of this patent, take the PS ball micro-structural of self assembly as mask, the SEM (ESEM) of the anti-reflection microstructure of constructing with the substrate of RIE etch silicon and the picture of cross section Electronic Speculum. Here take the PS ball of 460nm as the example introduction: picture (the gas SF of etching under the best etching condition of the flat scanning Electronic Speculum of the antireflection catoptric arrangement that figure A constructs as this method6(30sccm) and CHF3(6sccm), the power 100W of etching, chamber pressure 30mTorr, etch period 380s). Figure B is that the cross section ESEM picture scanning angle of such anti-reflection microstructure is 75 °.
The top platform that can find out cone from A figure is very little, and is close proximity between the adjacent cone, and such appearance is conducive to improve antireflective property very much. Owing to above this structure a little platform being arranged, can improve the mechanical performance of this micro-structural simultaneously, also be comparatively favourable to using. The average height that can measure cone from B figure is 400nm. The slope variation of sidewall that we find out this micro-structural from B figure simultaneously is than slowly, and variation tendency is conducive to the raising of antireflective property so slowly.
As shown in Figure 5, utilize the described method of this patent, construct the polystyrene nanospheres array of individual layer with self-assembling technique, by ESEM picture and the corresponding spectrogram with RIE etching constructing anti-reflection microstructure. Figure A is that etch period lack (260s) thereby so that the degree of depth of etching is littler, figure C etch period long (320s) causes the degree of depth decline of etching. Figure B is the ESEM picture of (290s) under time of best etching. Figure D is the not reverberation spectrogram of sample under the part simultaneously of silicon chip and etching. Chain-dotted line is the reflectance spectrum curve of etch period 260s among the figure, reflectivity is less than 10%, and solid line is the reflectance spectrum curve of etch period 290s among the figure, all lowest part is 1.2% to reflectivity less than 5%, the figure dotted line is etch period 320s three etching curves, reflectivity is less than 7%, and the reflectivity that black solid line is silicon chip among the figure is greater than 32%. We can find out that the anti-reflection microstructure that utilizes patented method to construct has good antireflective property from curve, and it can drop to 5% to the reflectivity of silicon chip, minimum can dropping to below 2% from 33%.
As shown in Figure 6, utilize the described method of this patent, construct monofilm polystyrene/nano particle micro-structural with self-assembling technique, the photo of the light microscope of the monocrystal silicon substrate by RIE etching constructing anti-reflection structure, the left side is the optical microscope photograph that the monocrystal silicon substrate surface of structure is arranged, the right side is the optical microscope photograph that does not have structure monocrystal silicon substrate surface, and relatively the right and left of this width of cloth optical photograph can find out that the antireflective property on the monocrystal silicon substrate of structure surface is arranged is better. The size of sample can be accomplished 2cm * 2cm.
As shown in Figure 7, utilize the described method of this patent, the array structure of the polystyrene take particle diameter as 1100nm is mask, obtains the anti-reflection microstructure that is suitable at wavelength 900～2400nm by the RIE etching. The left figure of Fig. 7 is the cross section ESEM picture of anti-reflection microstructure, its inclination angle is 75 °, and right figure is the spectrogram of anti-reflection microstructure, can find out that this structure antireflective property is better, its reflectivity reaches 3% less than 7% lowest part, compare with 33% reflectivity of silicon chip reduced a lot.
As shown in Figure 8, utilize the described method of this patent, with assembling amino substrate and put into the solution of Nano silver grain, utilize electrostatic force, the Nano silver grain of individual layer on substrate is assembled.
As shown in Figure 9, utilize the described method of this patent, take the single silver nanoparticle of self assembly as the RIE etching mask, obtain obtaining anti-reflection microstructure by the RIE etching, can find out that from ESEM structure has preferably taper, antagonistic reflex is more favourable.
Embodiment
Further illustrate the inventive method and application below by embodiment, rather than will limit the present invention with these embodiment.The present invention is a mask with the orderly nano particle of substrate surface mainly, by RIE (different etching conditions such as gas, power, chamber pressure) etching, realizes that different base is had constructing of antireflective property surface micro-structure.
PS ball aqueous solution can utilize 2% sodium dodecyl sulfate solution to form the ordered structure of individual layer on the water surface, and this single layer structure can be transferred in monocrystalline silicon [n type, (the 100)] substrate.(KluwerAcademicPublishers，Dordeecht.2003，p.163-172)。
The technical parameter of self-assembled monolayer ball: 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), get on the silicon chip that solution that 5 μ L prepare drips to the clean and hydrophilic treatment in surface, at this moment the PS microballoon scatter at the water surface and forms unordered structure, as Fig. 1 a, add the sodium dodecyl sulfate solution of 5 μ L2% behind the wait 50min, at this moment the PS ball will form orderly monolayer array on the water surface, as Fig. 1 b.Individual layer PS ball on the water surface is transferred on the silicon face, detected 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 anti-reflection 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 380s, the scanning electron microscope picture of the anti-reflection microstructure that obtains is as shown in Figure 4.
The silylating reagent of assembling last layer amino on silicon chip, utilize amino to adsorb Nano silver grain, so just in substrate, obtained a monofilm (S.Wang who can be used for the Nano silver grain of RIE etching barrier layer, X.Z.Yu, H.T.Fan, Appl.Phys.Lett.2007,91,061105 (1-3)).
The monocrystalline silicon of the clean dried handled is (or quartzy, glass) vacuum dryer that has dripped aminosilane reagents (trimethoxy third amino silane) is in advance put in substrate, keeping the vacuum tightness of vacuum dryer is 0.012Pa, toluene is used in taking-up successively after placing 40min, chloroform, the alcohol solvent ultrasonic cleaning, each 3min, use the deionized water ultrasonic cleaning again 2 times, each 3min, dry up with nitrogen then, the silicon chip that to modify the aminosilane reagents unimolecular film afterwards is immersed in literature method preparation (S.D.Stahaye, K.R.Patil, S.R.Padalkar, Materials research bulletin, 2001,36,24h in the solution of argent nano particle 1149-1155).So just in substrate, obtain nano grain of silver subarray as shown in Figure 8, utilize the RIE etching to obtain anti-reflection microstructure shown in Fig. 9 Electronic Speculum.Etching gas is CF
4(30sccm), the power 100W of etching, chamber pressure 30mTorr, etching time 5min, etch rate per minute 30nm.
Get 600mL high purity water (handle through French MILLI～Q ultrapure water instrument, resistivity is 18.2M Ω cm) and put into the glass container that diameter is 12cm, the annulus that to put a diameter on the water surface be the 10cm teflon.To the magnetic agitation in addition of the water surface in the annulus, its rotational speed is 120rpm, the water surface forms concave meniscus under the stirring of magnetic force, at this moment PS ball aqueous solution (Feng Pan, the JunyingZhang of Dropwise 5 % in concave meniscus, Chao Cai, and Tianmin Wang, Langmuir, 2006,22,7101-71014).The PS ball self-organization of the water surface forms the structure with orderly individual layer PS ball under centrifugal action, with vertical czochralski method the microstructure of orderly individual layer PS ball is transferred to (as the substrate through cleaning and hydrophilic treatment such as silicon, glass, polymkeric substance) in the substrate.Then the sample that obtains is prepared anti-reflection microstructure by the RIE etching, the gas SF of etching
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching time are 300S.The Electronic Speculum figure of PS ball array is similar to Fig. 3, and the Electronic Speculum figure of anti-reflection microstructure is similar to Fig. 4.
Can in the single crystalline Si substrate, prepare individual layer PS ball array structure with vertically lifting 2%PS microballoon aqueous process, its speed that vertically lifts be 10 μ m/s (H Chen, Suzuki, Sato Z, Appl.Phys.A, 20051999,81,1127-1130).With the PS ball array of this individual layer, by the surface of RIE etching acquisition anti-reflection microstructure, with shown in Figure 4 similar.The gas SF of etching
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching speed are 90nm/min, etching time is 4min.
With SiO
2Microballoon is the ink of micro-contact printing, transfers on the silicon base, obtains the SiO of six sides tightly packed (or non-tightly packed)
2The individual layer ball array of microballoon (X Yan, J Yao, G Lu, X Li, J Zhang, BYang, J.AM.CHEM.SOC.2005,127,7688-7689).Array with this individual layer silica spheres is a mask, by the RIE etching, just obtains having the surface of anti-reflection structure, scanning electron microscope picture and shown in Figure 4 similar.The condition of RIE etching is SF
6(30sccm) and O
2(5sccm) (SF
6: O
2=6: 1), the power 100W of etching, chamber pressure 30mTorr, the power 20W of ICP (regulating the parameter of cavity plasma intensity in the RIE etching), speed of etching is 200nm/min, etching time is 5min, can improve like this and select ratio.
Embodiment 6
Utilize the method for electro-deposition on silicon base, to obtain the unordered nano grain of silver subarray of individual layer, the picture of scanning electron microscope and similar (deposition voltage of 1% silver nitrate aqueous solution, 200mV, supporting electrolyte 5% potassium nitrate, electrode separation 1cm) shown in Figure 8.With this structure is that RIE is an etching barrier layer, just obtains having the surface of anti-reflection structure in substrate, scanning electron microscope picture and shown in Figure 9 similar.The condition etching gas of etching is CF
4(30sccm), the power 100W of etching, chamber pressure 30mTorr, etching speed are 30nm/min, etching time is 8min.
Embodiment 7
Buy the PS solution of massfraction 10% from Microparticles GmbH (Germany), mix with ethanol with equal-volume, 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 just scatter at the water surface and forms unordered structure, b step as Fig. 1, wait for the solution that adds the lauryl sodium sulfate of 5 μ L 2% behind the 50min, at this moment will on the water surface, form the oldered array of individual layer.Individual layer PS ball on the water surface is transferred on the PMMA substrate surface, so just obtained the single layer structure of PS ball on polymeric substrates, its scanning electron microscope picture and Fig. 3 are similar.PS ball with individual layer is the mask of RIE etching, and the etch polymers substrate so just obtains anti-reflection microstructure on polymeric substrates, and its scanning electron microscope picture is similar to Fig. 4.The condition of RIE etching: etching gas is Ar (10sccm) and O
2(5sccm) (Ar: O
2=2: 1), the power 60W of etching, chamber pressure 30mTorr, etching speed are 30nm/min, etching time is 7min.
Embodiment 8
Buy 10% PS solution to mix excusing from death 15min with ethanol with equal-volume stand-by from Microparticles GmbH (Germany).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 with regard to the water surface and forms with unordered structure such as Fig. 1 b step, what add 5 μ L 2% behind the wait 50min is the solution of sodium alkyl sulfate, and this is the orderly array that will form on the water surface with orderly individual layer.Individual layer PS ball on the water surface is transferred on the glass surface, and its scanning electron microscope picture of single layer structure of PS ball that so just obtains an individual layer on substrate of glass is shown in Figure 3 similar.PS ball with individual layer is the mask of RIE etching, and the etching glass substrate so just obtains anti-reflection microstructure on substrate of glass, so its scanning electron microscope picture is similar to Fig. 4.The condition of RIE etching is that the condition etching gas of etching is CF
4(15sccm) and O
2(5sccm) (CF
4: O
2=3: 1), the power 60W of etching, chamber pressure 30mTorr, etching speed are 30nm/min, etching time is 6min.
Embodiment 9
Utilize the method for electro-deposition can on silicon base, obtain the orderly PS micro-sphere array of individual layer, the picture of scanning electron microscope and similar (deposition voltage of 2%PS aqueous solution, 600mv, electrode separation 1cm) shown in Figure 2.The PS nano particle moves (Won.Mook, Choi.Park, Nanotechnology to the silicon electrode plate direction under the electric field force effect, 2006,17,325-329), so just on pole plate, obtain the array of the PS nano particle of individual layer, its scanning electron microscope and shown in Figure 3 similar.Then the sample that obtains is prepared anti-reflection microstructure by the RIE etching, the gas SF of etching
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching time are 220S.So just in substrate, obtain the anti-reflection microstructure surface, its scanning electron microscope picture and shown in Figure 4 similar.
With oneself PS nano particle spin coating on silicon base of synthetic 1% obtain structure and shown in Figure 3 similar (R.A.Weiss, X.Zhai, A.V.Dobrynin, Langmuir 2008,24,5218-5220).With this structure is that RIE is an etching barrier layer, just obtains having the surface of anti-reflection structure in substrate, scanning electron microscope picture and shown in Figure 4 similar.The condition etching gas of etching is SF
6(20sccm) and O
2(5sccm) (SF
6: O
2=4: 1), the power 50W of etching, chamber pressure 30mTorr, etching speed are 150nm/min, etching time is 6min.
Embodiment 11
With vertically lifting 2%SiO
2The aqueous process of microballoon can obtain individual layer SiO in the single crystalline Si substrate
2Micro-sphere array, its speed that vertically lifts be 5 μ m/s. (H Chen, Suzuki, Sato Z, Appl.Phys.A, 20051999,81,1127-1130).SiO with this individual layer
2Micro-sphere array is by the surface of etching acquisition anti-reflection microstructure, with shown in Figure 4 similar.The gas SF of etching
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching speed are 40nm/min, etching time is 5min.
Embodiment 12
Can on substrate of glass, obtain individual layer PS ball array with vertically lifting 2%PS microballoon aqueous process, its speed that vertically lifts be 10 μ m/s. (H Chen, Suzuki, Sato Z, Appl.Phys.A, 20051999,81,1127-1130).With the PS ball array of this individual layer, by the surface of etching acquisition anti-reflection microstructure, with shown in Figure 4 similar.The gas CF of etching
4(30sccm) and O
2(6sccm) (CF
4: O
2=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching speed are 15nm/min, etching time is 330S.
Embodiment 13
Microparticles GmbH (Germany) locates to buy 10% PS solution, and to mix excusing from death 15min with ethanol with equal-volume stand-by.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 with regard to the water surface and forms with unordered structure such as Fig. 1 b step, what add 5 μ L 2% behind the wait 50min is the solution of sodium alkyl sulfate, and this is the orderly array that will form on the water surface with orderly individual layer.Individual layer PS ball on the water surface is transferred on the quartz surfaces, and its scanning electron microscope picture of single layer structure of PS ball that so just obtains an individual layer on quartz substrate is shown in Figure 3 similar.PS ball with individual layer is the mask of RIE etching, and the etching quartz substrate so just obtains anti-reflection microstructure on quartz substrate, so its scanning electron microscope picture is similar to Fig. 4.Etching gas is CF
4(15sccm) and O
2(5sccm) (CF
4: O
2=3: 1), the power 60W of etching, chamber pressure 30mTorr, etching speed are 30nm/min, etching time is 7min.
Embodiment 14
Utilize the method for electro-deposition can on silicon base, obtain the orderly argent nano particles array of individual layer, the picture of scanning electron microscope and similar (deposition voltage of 1% silver nitrate aqueous solution, 800mV, electrode separation 1cm) shown in Figure 8.Silver ion reduction is the simple substance Nano silver grain under the electric field force effect, so just obtains the array of the Nano silver grain of individual layer on silicon electrode plate, its scanning electron microscope and shown in Figure 8 similar.Then the sample that obtains is prepared anti-reflection microstructure by the RIE etching, the gas SF of etching
6(30sccm) and CHF
3(6sccm) (SF
6: CHF
3=5: 1), the power 100W of etching, chamber pressure 30mTorr, etching time are 280S.So just in substrate, obtain the anti-reflection microstructure surface, its scanning electron microscope picture and shown in Figure 9 similar.
Microparticles GmbH (Germany) locates to buy 10% PS solution, and to mix excusing from death 15min with ethanol with equal-volume stand-by.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 with regard to the water surface and forms with unordered structure such as Fig. 1 b step, wait for add behind the 50min 5 μ L, 2% be the solution of sodium alkyl sulfate, this is the orderly array that will form on the water surface with orderly individual layer.Individual layer PS ball on the water surface is transferred on the alundum (Al surface, so just obtained the single layer structure of the PS ball of an individual layer in the alundum (Al substrate, its scanning electron microscope picture is shown in Figure 3 similar.PS ball with individual layer is the mask of RIE etching, and the substrate of etching alundum (Al so just obtains anti-reflection microstructure in the alundum (Al substrate, so its scanning electron microscope picture is similar to Fig. 4.Etching gas is Ar (20sccm) and O
2(7sccm) (Ar: O
2=2.9: 1), the power 60W of etching, chamber pressure 20mTorr, etching speed are 20nm/min, etching time is 8min.
Claims (10)
1. be the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, its step is as follows:
A chooses substrate, and substrate is cleaned and hydrophilicity-imparting treatment;
B, the method by self-assembling technique, function adsorption method or electro-deposition is assembled into the individual layer nano particle in the substrate, thereby obtains the array structure of the nano particle of individual layer in substrate, and its cycle is 100nm～10 μ m;
C is the restraining barrier of reactive ion etching with the array structure of individual layer nano particle, etching is carried out in substrate, thereby obtain the structure with antireflective property of taper in substrate.
2. as claimed in claim 1 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: substrate is silicon, glass, quartz, polymkeric substance or metal and metal oxide substrate.
3. as claimed in claim 2 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: at the bottom of polymeric substrates is dimethyl silicone polymer, polyurethane, Polyvinylchloride, polyethylene terephthalate, polystyrene, tygon, polypropylene or diazonium photoresist or polymethyl methacrylate base.
4. as claimed in claim 2 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: metallic substrates is gold, silver, platinum or aluminium substrate.
5. as claimed in claim 2 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: the metal oxide substrate is alundum (Al, zinc paste or titania substrate.
6. as claimed in claim 1 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: the individual layer nano particle is the nano particle of polymer nano-microspheres, silicon dioxide nanosphere, metal or metal oxide.
7. as claimed in claim 6 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: polymer nano-microspheres is pipe/polyhenylethylene nano microballoon or polymethyl methacrylate nano microballoon, the nano particle of metal is gold or silver-colored nano particle, and the nano particle of metal oxide is the nano particle of zinc paste, titania, di-iron trioxide or manganese dioxide.
8. as claimed in claim 1 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: the gas of polymeric substrates reactive ion etching is the mixed gas of argon gas and oxygen, its volume ratio is 0.2: 1～5: 1, the power of etching is 30～80W, the time 200～800S of etching.
9. as claimed in claim 1 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: the gas of silicon, quartz, substrate of glass reactive ion etching is SF
6And CHF
3, CF
4And O
2Or CF
6And O
2Mixed gas, or CF
4, the volume ratio of mixed gas is 1: 1～7: 1, and etching power is 30～100W, and etching time is 200～600S.
10. as claimed in claim 1 is the method for etching barrier layer constructing anti-reflection microstructure with the individual layer nano particle, it is characterized in that: the gas of metal and metal oxide substrate reactive ion etching is Ar or Ar and O
2Mixed gas, the volume ratio of mixed gas is 0.2: 1～7: 1, etching power 30～150W, etching time 300～500S.
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