CN100576439C - Method at the substrate surface constructing anti-reflection structure - Google Patents
Method at the substrate surface constructing anti-reflection structure Download PDFInfo
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- CN100576439C CN100576439C CN200810050830A CN200810050830A CN100576439C CN 100576439 C CN100576439 C CN 100576439C CN 200810050830 A CN200810050830 A CN 200810050830A CN 200810050830 A CN200810050830 A CN 200810050830A CN 100576439 C CN100576439 C CN 100576439C
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Abstract
The present invention relates to utilize LB technology or self-assembling technique on monocrystal silicon substrate, to form organic molecular monolayer film figure, and be mask with this monofilm pattern, carry out wet etching, have the surface of sub-wavelength conical structure in monocrystalline silicon surface formation, thereby make monocrystal silicon substrate have the method for antireflective property.Material surface by the described method of this patent obtains in the scope of 400～2400nm wavelength, can obtain the reflectivity less than 5%.This substrate surface can be avoided reflection of light effectively, improves the efficiency of light energy utilization, reduces unwanted reflection interference, improves sensing sensitivity.The described method constructing anti-reflection structure of this patent has the advantages that cost is low, technology is simple, productive rate is high, has stronger practicality.There is good antireflective property on this surface with sub-wavelength conical structure, therefore has very important use at aspects such as solar cell, white light sensing display, photoelectric device, optical mirror slips.
Description
Technical field
The micro-structural that the invention belongs to patterned surface is constructed technology, be specifically related to utilize LB technology or self-assembling technique on monocrystal silicon substrate, to form organic molecular monolayer film figure, and be mask with this monofilm pattern, carry out wet etching, have the surface of sub-wavelength conical structure in monocrystalline silicon surface formation, thereby construct out underlying structure with antireflective property.
Background technology
The reflectivity of monocrystal silicon substrate is higher, makes the reflection of incident light rate be higher than 35%, has had a strong impact on the performance of the optics and the photoelectricity device of monocrystal silicon substrate, for example solar cell, display, optical pickocff etc.In order to improve the performance of these devices, need to reduce monocrystal silicon substrate surface reflection light loss.Tradition reduces the loss of monocrystalline silicon surface reverberation and utilizes refraction coefficient continually varying plural layers mostly; but this plural layers through regular meeting because thermodynamics does not match or problem such as adhesive force has reduced the stability of plural layers; and this plural layers are only relatively good at the antireflective property of certain wave band usually, and can not realize the reduction reverberation loss than long-wave band.
Since 1967, Bernhard finds that first the compound eye surface of moth is that array of protrusions by the sub-wavelength yardstick constitutes, and propose these protruding structures and can reduce reflection of light (Endeavor 16, p.76-84,1967), scientists has been attempted the anti-reflection structure that several different methods is constructed this sub-wavelength yardstick.The principle of this anti-reflection structure is that the micro-structural of projection is equivalent to a refraction coefficient continually varying dielectric layer, therefore has reasonable antireflective property.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 antireflective property (U.S.P at.No.4,013,465) is all arranged in than polarizers of big angle scope.Structure with antireflective property not only is confined to the structure in this regular cycle, people such as Gombert utilize the method for interfering etching to construct out the pattern of the compound eye structural of regular moth earlier, the part of utilizing methods such as mechanical friction to construct out random structure again, this two parts combination, also can effectively reduce reverberation loss (U.S.Pat.No.6,359,735).Antireflective property is not only relevant with the shape of structure, also relevant with factors such as the cycle of structure and the degree of depth, in 2003, human metals such as Takahara are made mask, and evaporation forms lattice structure, uses plasma etching (RIE) then, in the process of etching, the metal lattice size diminishes gradually, and then forms the pyramidal structure of high length-diameter ratio, and this structure has good antireflective property (U.S.Pat.No 20030102286).
The method that tradition is constructed the sub-wavelength structure anti-reflecting surface mainly contains: electron beam lithography, nano impression are done and are carved etching, laser interference etching etc.Report has constructing of antireflective property surface in order to realize in the document, and science and scientific workers have carried out a lot of research work, 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 accuracy, advantages such as high-resolution are because shortcoming such as instrument costliness, efficient be lower has restricted it and used widely.Etching method at dried quarter behind laser interference etching and the nano impression can be constructed out anti-reflecting surface (the Nanotechnology 2000.11.161 of sub-wavelength structure in the large tracts of land scope; 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.
Bibliographical information in recent years, based on spin coating technique, chemical vapour deposition technique, the electron beam evaporation plating technology, simple, cheap relatively metal film self-assembling technique etc. is used to construct the anti-reflecting surface of sub-wavelength structure.It is reported and utilize the formed island of metal film, etching is carried out in substrate, can form surface with anti-reflection structure as mask with high density self assembly characteristic.2007, people such as Sen Wang utilized the silver-colored island that deposits on silicon base to carry out dry etching for mask, construct out the surface (Appl.Phys.Lett.2007.91.061105) with anti-reflection structure.People such as PengJiang utilize the titanium dioxide silicon island to be mask, obtain the orderly pattern of chromium with electron beam 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 the spin coating technology to form the titanium dioxide silicon island 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 is more complicated all, has equally also limited its application.
Related unorthodox method is to utilize the self assembly of organic molecule to form the monofilm technology in this patent, is mask with the monofilm of this patterning, carries out wet etching, constructs the array structure of taper.This construction method cost is low, and can realize constructing of large area anti-reflection structure, can be widely used in aspects such as solar cell, white light sensing display, photoelectric device, optical mirror slip.
Summary of the invention
The purpose of this invention is to provide a kind of method at the substrate surface constructing anti-reflection structure, it is by making organic molecule (as stearic acid, two palmitic acid phosphatid ylcholine DPPC, two myristoyl phosphatid ylcholine DMPC etc.) form the pattern of island on monocrystal silicon substrate, then by the alkaline solution etching, form the conical surfaces structure, can effectively reduce the reverberation loss.
We find after deliberation, utilize the constructed anti-reflection structure of this method, can significantly reduce the reflectivity of material surface.As shown in Figure 6, (in 400～2400nm) scopes, the surface reflectivity of polished silicon is greater than 35%, and by the resulting material surface of the method that this patent provided at visible light and near-infrared wavelength, in the scope of this wavelength, can obtain reflectivity less than 5%.The substrate surface that the described method of this patent is constructed can be avoided reflection of light effectively, improves the efficiency of light energy utilization, reduces unwanted reflection interference, improves sensing sensitivity.
The method constructing anti-reflection structure cost that utilizes this patent to provide is low, and technology is simple, and the productive rate height, has stronger practicality.There is good antireflective property on this surface with sub-wavelength conical structure, therefore has very important use at aspects such as solar cell, white light sensing display, photoelectric device, optical mirror slips.
The described method with anti-reflection structure surface of constructing of this patent may further comprise the steps:
A chooses monocrystal silicon substrate, and clean is carried out in substrate;
B, go out the island-shaped pattern of organic molecule monofilm at the surface construction of monocrystal silicon substrate by LB technology or self-assembling technique, the height on island is 2～5nm, the cycle of this nanometer micrometer structure can be regulated and control with different experiment parameters by adopting different technology, and nanometer micrometer structure of the present invention can be realized the regulation and control between 500nm～15 μ m;
C, in alkaline solution (NaOH, KOH or TMAH (Tetramethylammonium hydroxide)), etching is carried out in the substrate of organic molecule monofilm pattern, regulate and control the degree of depth, the shape of etching by changing concentration of lye, temperature and etch period, obtain the body structure surface with antireflective property of taper or back taper;
Have an anti-reflection structure surface through above step is resulting,, can observe light reflectivity and obviously descend by the determination and analysis of atomic force microscope, ESEM and ultraviolet spectra.
Monocrystal silicon substrate ([n type, or [p type (100)], (100)] clean): the clean of substrate mainly contains two kinds of methods, first method is at first with the oxygen plasma system substrate surface to be handled, purpose is to remove the organic substance of surface adsorption, oxygen gas flow rate 80～200ml/min, power 100～300W, processing time 1～15min; 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=1～2: 1～3: 1～7, soaking 20～120min under 40～130 ℃ 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.
Constructing organic molecule monofilm method of patterning on monocrystal silicon substrate is LB technology or self-assembling technique.
Concrete step is as follows:
The LB technology: with micro syringe with an amount of V
0(2～50 μ l), finite concentration C
1(0.1～10mg/ml) sample (amphiphilic straight chain molecule such as two palmitic acid phosphatid ylcholines, two myristoyl phosphatid ylcholines, stearic acid or mol ratio are 1～10: 1 palmitic acid that mixes and the tar acid that holds with both hands with both hands) solution spreads over high purity water and (handles through French MILLI～Q ultra-pure water instrument, resistivity is 18.2M Ω cm) on the parfacies, treat solvent a period of time t that volatilizees naturally
1(behind the 10min～24h), on LB film balance (the Britain 312D of Nima company film balance), with baffle plate with certain speed S
1(5～30cm
2/ min) compress, obtain the Π～A curve of this sample, with the surface pressure of film in the Wihelmy film balance measurement compression process, (1～30mN/m), certain hour t keep-ups pressure to select suitable shift pressure P according to Π～A curve then
2(10min～24h), the monocrystal silicon substrate or the NH that cross in the oxygen plasma system handles of big water gaging flushing with vertical czochralski method
3H
2O and H
2O
2The monocrystal silicon substrate handled of mixed solution on lift individual layer Langmuir film, putting forward film speed is S
2(1～50mm/min), whole process system temperature is controlled at room temperature (24 ℃ ± 3 ℃).Because there is the solid-state platform that changes to fluid-like state of class in employed amphiphatic molecule, shift this molecule can form island structure on monocrystal silicon substrate pattern under the pressure of and fluid-like state coexistence solid-state in class.Be illustrated in figure 3 as the atomic force microscope picture that shifts the stearic acid molecule by said method, the island is by the solid-state molecular composition of class, and the part around the island is the molecule of fluid-like state, the height 2～5nm on island, and adjacent two island centre distances are 500nm～15 μ m.
Self-assembling technique: self-assembly method is that to immerse concentration be in the target solution of silane of 0.1～10 μ g/ml to the monocrystal silicon substrate of the clean dried that will handle, as silicol (silanol etc.), alkyl silane (n-octyl dichlorosilane, octadecyl trichlorosilane etc.), amino silane (aminopropyl triethoxysilane, hmds etc.) etc., toluene is used in taking-up successively after soaking 20s～24h, 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 on monocrystal silicon substrate, obtain being modified with the pattern of single thin film island structure, height 2～the 5nm on island, center, adjacent two island apart from 500nm～15 μ m, result and shown in Figure 3 similar.
Method shown in this patent can be reduced to monocrystalline silicon surface below 5% about the reflectivity of 400～2400nm wave band is by 35%, has effectively reduced catoptrical loss.And this method can be used for constructing large-area anti-reflection structure, and cost is low, and the efficient height meets industrialized standard, can be used for photoelectric devices such as solar cell, white light sensing display, reduces device cost greatly.
Description of drawings:
Fig. 1: the Experimental equipment of utilizing alkaline solution etching monocrystalline silicon surface;
Fig. 2: the key step schematic diagram on constructing anti-reflection structure surface;
Fig. 3: embodiment 1 obtains utilizes the atomic force microscope photo of the substrate surface that the LB technology constructs;
The ESEM picture of the anti-reflection structure substrate surface that Fig. 4: embodiment 1 obtains;
The optical microscope photograph of the anti-reflection structure substrate surface that Fig. 5: embodiment 1 obtains and the optical microscope photograph that does not have anti-reflection structure single crystal substrates surface;
The reflectance spectrum of the anti-reflection structure substrate surface that Fig. 6: embodiment 1 obtains and the reflectance spectrum that does not have the monocrystal silicon substrate surface of anti-reflection structure;
The ESEM picture of the back taper anti-reflection structure substrate surface that Fig. 7: embodiment 2 obtains.
As shown in Figure 1, the Experimental equipment of alkaline solution etching monocrystalline silicon surface, 11 is temperature control sample table, 12 is water-bath, and 13 are the sample of etching (being the monocrystal silicon substrate of finishing organic molecule monofilm), and 14 is plastic beaker, 15 is test tube clamp, 16 is thermocouple, and 17 is iron stand, and 18 is magnetic stir bar.
The installation drawing of the alkali lye etching of using in this patent as shown in Figure 1, on the temperature control sample table 11 of thermocouple 16 control temperature (error ± 1 ℃), carry out the water-bath heating, with finite concentration (0.001～10mol/L, the concentration of alkaline solution is 0.01～10mol/L further, again further the concentration of alkaline solution be 0.05～10mol/L) alkaline solution such as KOH solution be contained in 300mL plastic beaker 14 in, the temperature (20～80 ℃) of control water-bath, regulate simultaneously magnetic stir bar 18 speed (100～800 change/min).In etching process, monocrystal silicon substrate and alkaline solution reaction can produce silicate, can make the silicate product break away from silicon face by stirring, and reduce the roughness of sample surfaces.Monocrystal silicon substrate is bonded on the thin slice of plastics by adhesive tape, and is fixed on test tube clamp 15 on the wall of plastic beaker 14.Because the alkaline solution etching has the etch rate ratio of higher (100)/(111) crystal face, make and do under the condition of mask at suitable monofilm pattern, can etching form the array structure of taper, improve antireflective property greatly.By regulating the concentration of KOH solution, the time of etching, (2min～2h) and the bath temperature of etching were regulated the degree of depth of etching, and then regulate the antireflective property of monocrystal silicon substrate.Along with the increase of etch period, the degree of depth of etching increases, and the flat-top area of the cone that obtains reduces gradually, forms the cone of point at last, and the degree of depth of cone can reach 700nm, as shown in Figure 4.The alkaline solution of etch silicon can also be used NaOH solution or TMAH solution such as (Tetramethylammonium hydroxide).
As shown in Figure 2, utilize the LB technology to construct the picture on surface of monofilm, the step schematic diagram of etching constructing anti-reflection structure in alkaline solutions such as KOH.The A step is to shift the parental type organic molecule on monocrystal silicon substrate, 21 for needing the monocrystal silicon substrate of constructing anti-reflection structure, and 22 is the solid-state molecule of class in the organic monolayer film, and molecules align is tightr, 23 is the molecule of fluid-like state in the organic monolayer film, and molecules align is more loose.The B step is a mask for the monofilm with this patterning, etching in KOH solution.Wherein, 22 parts can effectively stop KOH solution because molecules align is tightr, and 23 parts are because molecules align is more loose, and KOH solution can soak into monocrystalline silicon surface, so etching away by selectivity.Because silicon chip etching in alkaline solution is an anisotropic etching, be 100: 1 at (100) crystal face with (111) crystal face etch rate ratio, so can form the structure of cross section V-arrangement.So, when being the mask etching monocrystal silicon substrate, can obtain the structure of taper with the island structure, the structure of this taper is equivalent to insert the multilayer film that refraction coefficient changes step by step between monocrystalline silicon surface and air, effectively improves antireflective property.
As shown in Figure 3, corresponding embodiment 1 utilizes the LB technology to construct the atomic force microscope photo of the monofilm of patterned surface, and its sweep limits is 10 μ m * 10 μ m.Part (dark colour part) dark among the figure is the solid-state organic molecule of class, and bright part (light colour part) is the organic molecule of fluid-like state.
As shown in Figure 4, corresponding embodiment 1 utilizes the described method of this patent, the ESEM picture of the anti-reflection structure that the surface micro-structure of constructing monofilm with the LB technology is constructed by KOH solution etching.A figure is the flat scanning Electronic Speculum picture of this anti-reflection structure, and B figure is that the inclination angle is the cross section surface sweeping Electronic Speculum picture of 70 degree.Scheme as can be seen from A that the top of cone is sharp, and be close proximity between the adjacent cone, such appearance helps improving antireflective property very much.The average height that can measure cone from B figure is 700nm.
As shown in Figure 5, corresponding embodiment 1, utilize the described method of this patent, construct the surface micro-structure of monofilm with the LB technology, the digital camera photo of the monocrystal silicon substrate by KOH solution etching constructing anti-reflection structure, and with the digital camera photo that does not have structure monocrystal silicon substrate surface relatively, have the antireflective property on monocrystal silicon substrate surface of structure better as can be seen.Left side figure is the digital camera photo that the monocrystal silicon substrate surface of structure is arranged, and right figure is the digital camera photo that does not have structure monocrystal silicon substrate surface.The size of two samples all is 2cm * 2cm.
As shown in Figure 6, corresponding embodiment 1 utilizes the described method of this patent, constructs surperficial little knot of monofilm with the LB technology, the reflectance spectrum of the anti-reflection structure of constructing by KOH solution etching.The a curve is the reflectance spectrum that does not have the silicon chip surface of anti-reflection structure, and the b curve is the reflectance spectrum of the silicon face of constructing anti-reflection structure.Explanation on the monocrystal silicon substrate surface that does not have anti-reflection structure to the reflection of light rate greater than 35%, by structure reflectivity is reduced to below 5% at the wave band of 400～2400nm, has effectively reduced catoptrical loss in the taper of monocrystal silicon substrate surface construction.
As shown in Figure 7, corresponding embodiment 2 utilizes the described method of this patent, constructs the ESEM picture of the surface micro-structure of monofilm by resultant back taper surface texture in the KOH solution (1mol/L) of higher concentration with the LB technology.When KOH concentration was higher, etch rate was bigger, the structure of easier formation back taper, and the surface texture of this back taper also has antireflective property preferably.A figure is the flat scanning Electronic Speculum picture of this anti-reflection structure, and B figure is that the inclination angle is the cross section surface sweeping Electronic Speculum picture of 70 degree.
Specific implementation method
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 monofilm of silicon face mainly, by etching in alkaline solution (KOH, NaOH or TMAH), realizes having constructing of antireflective property surface micro-structure.
Embodiment 1:
The stearic acid molecule can be with the stearic acid molecular transfer on mica substrate with the LB technology when fluid-like state and the solid-state coexistence of class, and form island structure (L.F.Chi, M.Gleiche, and H.Fuchs Langmuir 1998,14,875-879).We shift stearic acid (purity 〉=99%, monofilm Fluk) with the LB technology in monocrystalline silicon [n type, (100)] substrate.
The preparation parameter of LB film: V
0=25 μ l, C
1=1mg/ml, CHCl
3Solution, t
1=10min,
S
1＝15cm
2/min，P＝21mN/m，t
2＝15min，S
2＝4mm/min
With atomic force microscope Tapping pattern observation island structure, as shown in Figure 3.As can be seen from the figure, in the structure on this island, the part on island is made of the solid-state stearic acid molecule of class, and the part in sea has the stearic acid molecule of fluid-like state to constitute.To be dipped into concentration be 0.1molL to the silicon chip that this monofilm is modified then
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, uses ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min, dry up with high purity nitrogen, just obtain having the surface of anti-reflection structure, its surface sweeping Electronic Speculum picture as shown in Figure 4.
Embodiment 2:
It is 1molL that the monocrystal silicon substrate [n type, (100)] of monofilm modification among the embodiment 1 is dipped into concentration
-1Temperature is etching 4min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min, dry up with high purity nitrogen, just obtain the body structure surface with antireflective property of back taper, its surface sweeping Electronic Speculum picture as shown in Figure 7.
Embodiment 3:
Two palmitic acid phosphatid ylcholine DPPC are when fluid-like state and the solid-state coexistence of class, it can be transferred on the monocrystal silicon substrate [n type, (100)] with the LB technology, and form island structure (C.W.McConlogue and T.K.Vanderlick Langmuir 1999,15,234-237).To be dipped into concentration be 0.1molL to the silicon chip that this monofilm is modified then
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain having the surface of anti-reflection structure, with shown in Figure 4 similar.
Embodiment 4:
Two myristoyl phosphatid ylcholine DMPC are when fluid-like state and the solid-state coexistence of class, it can be transferred on the monocrystal silicon substrate [n type, (100)] with the LB technology, and form island structure (C.W.McConlogue and T.K.Vanderlick Langmuir 1999,15,234-237).To be dipped into concentration be 0.1molL to the silicon chip that this monofilm is modified then
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain having the surface of anti-reflection structure, with shown in Figure 4 similar.
Embodiment 5:
Palmitic acid (C
15H
31COOH) and the tar acid (C that holds with both hands with both hands
23H
47COOH) mixture control mol ratio 5: 1, lift into the individual layer hybrid films with the LB technology, tar acid and the palmitic acid meeting on the gas-liquid two-phase interface that holds with both hands with both hands be separated, form micron submicron order sea-island planar structure, the monofilm of this sea--island structure can be transferred to (K.Ekelund, E.sparr on the silicon base in the process of lifting, J.Engblom, H.Wennerstrom and S.Engstrom.Langmuir 1999,15,6946～6949).Monofilm pattern with this island is a mask, is 0.1molL in concentration
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain having the surface of anti-reflection structure, ESEM picture and shown in Figure 4 similar.
Embodiment 6:
Control liquid phase built-up time can make alkyl silane reagent (OTS) part be assembled into monocrystalline silicon surface, and remainder still is exposed monocrystalline silicon surface (K.Ekelund, M.Grunze, A.A Baski, L.F.Chi, W.Schrepp, and H.Fuchs Langmuir 1995,11,2143～2150).Monofilm pattern with this island is a mask, is 0.1molL in concentration
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain having the surface of anti-reflection structure, ESEM picture and shown in Figure 4 similar.
Embodiment 7:
Monocrystal silicon substrate [the n type of monofilm modification among the embodiment 1, (100)] being dipped into concentration is 10%, temperature is etching 10min in 60 ℃ the TMAH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain the body structure surface with antireflective property of taper, its surface sweeping Electronic Speculum picture is shown in Figure 4 similar.
Embodiment 8:
Monocrystal silicon substrate [the n type of monofilm modification among the embodiment 1, (100)] being dipped into concentration is 0.1mol/L, temperature is etching 10min in 60 ℃ the NaOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain the body structure surface with antireflective property of taper, its surface sweeping Electronic Speculum picture is shown in Figure 4 similar.
Embodiment 9:
Go up transfer stearic acid (purity 〉=99%, monofilm Fluk) with the LB technology in monocrystal silicon substrate [P type, (100)].
The preparation parameter of LB film: V
0=25 μ l, C
1=1mg/ml, CHCl
3Solution, t
1=10min,
S
1＝15cm
2/min，P＝21mN/m，t
2＝15min，S
2＝4mm/min
With atomic force microscope Tapping pattern observation island structure, with shown in Figure 3 similar.To be dipped into concentration be 0.1molL to the silicon chip that this monofilm is modified then
-1, temperature is etching 10min in 60 ℃ the KOH solution, the speed of regulating magnetic stir bar simultaneously is 300 commentaries on classics/min, use ultra-pure water ultrasonic cleaning 3 times (70W) again, each 5min dries up with high purity nitrogen, just obtain having the surface of anti-reflection structure, its surface sweeping Electronic Speculum picture and shown in Figure 4 similar.
Claims (4)
1, in the method for substrate surface constructing anti-reflection structure, its step is as follows:
A, choose monocrystal silicon substrate, clean is carried out in substrate;
B, go out the island-shaped pattern of organic molecule monofilm at the surface construction of monocrystal silicon substrate by LB technology or self-assembling technique, the height 2～5nm on island, adjacent two island centre distances are 500nm～15 μ m;
C, in alkaline solution, etching is carried out in the substrate of organic molecule monofilm pattern, regulate and control the degree of depth, the shape of etching, obtain the body structure surface with antireflective property of taper or back taper by the concentration, temperature and the etch period that change alkaline solution;
Wherein said clean to substrate, at first be substrate surface to be advanced to handle with the oxygen plasma system, purpose is to remove the organic substance of surface adsorption, oxygen gas flow rate 80～200ml/min, power 100～300W, processing time 1～15min, again with high purity water to substrate surface ultrasonic cleaning 2～3 times, each time is 2～5min, makes thoroughly cleaning of surface; Or be NH in volume ratio
3H
2O: H
2O
2: H
2In the solution of O=1～2: 1～3: 1～7, soaking 20～120min under 40～130 ℃ 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, each time is 2～5min, makes thoroughly cleaning of surface;
The LB technology is with two palmitic acid phosphatid ylcholines, two myristoyl phosphatid ylcholines or the stearic acid amphiphilic straight chain molecule of micro syringe with 2～50 μ l, 0.1～10mg/ml, or mol ratio is that the mixed solution of 1～10: 1 the palmitic acid and the tar acid that holds with both hands with both hands spreads on the high purity water parfacies, treat that solvent volatilizees behind 10min～24h naturally, on the LB film balance, use baffle plate with 5～30cm
2The speed compression of/min, obtain the π～A curve of this sample, measure the surface pressure of film in the compression process with the Wihelmy film balance, selecting suitable shift pressure according to π～A curve then is 1～30mN/m, keep 10min～24h, on the monocrystal silicon substrate that cleaning surfaces is handled, lift individual layer Langmuir film with vertical czochralski method, putting forward film speed is 1～50mm/min, whole process system temperature is controlled at 21～27 ℃ of room temperatures, thereby on monocrystal silicon substrate, form the pattern of island structure, the island is by the solid-state molecular composition of class, and the part around the island is the molecule of fluid-like state;
Self-assembly method is that the monocrystal silicon substrate of the drying of clean is immersed concentration is in the target solution of silane of 0.1～10 μ g/ml, soak to take out after 20 seconds～24 hours and use toluene, chloroform, alcohol solvent ultrasonic cleaning successively, each 2～15min, use the deionized water ultrasonic cleaning again 2～3 times, each 2～15min, dry up with nitrogen then, thereby on monocrystal silicon substrate, obtain being modified with the island structure pattern of single thin film.
2, the method at the substrate surface constructing anti-reflection structure as claimed in claim 1 is characterized in that: alkaline solution is KOH solution, NaOH solution or TMAH solution.
3, the method at the substrate surface constructing anti-reflection structure as claimed in claim 1 is characterized in that: the concentration of alkaline solution is 0.001～10mol/L, and temperature is 20～80 ℃, and mixing speed is 100～800 commentaries on classics/min, and etch period is 2min～2h.
4, claim 1,2 or 3 described on the prepared surface of substrate surface constructing anti-reflection structure method in the application aspect solar cell, display or the optical pickocff.
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| WO2011156977A1 (en) * | 2010-06-19 | 2011-12-22 | 常州天合光能有限公司 | Method for manufacturing light trapping textured surface of polysilicon solar cell |
| CN104681421B (en) * | 2013-11-27 | 2017-11-10 | 中芯国际集成电路制造(上海)有限公司 | A kind of method for improving wet etching efficiency |
| CN103762160B (en) * | 2014-01-28 | 2017-05-10 | 北京华力创通科技股份有限公司 | Deep silicon etching method |
| CN104465821B (en) * | 2014-12-25 | 2017-11-24 | 胡明建 | A kind of design method of conical isometric matrix arranged solar plate |
| CN106199778B (en) * | 2016-09-18 | 2019-02-26 | 武汉华星光电技术有限公司 | A kind of preparation method of moth eye microstructure substrate |
| CN106583918B (en) * | 2016-11-30 | 2018-04-20 | 杭州电子科技大学 | Silicon substrate surface form is changed based on laser and controls the research method of forming technique |
| CN107219722A (en) * | 2017-05-19 | 2017-09-29 | 湖北知本信息科技有限公司 | The preparation method of high anti-reflection surface micro-structure and the micro-structural of preparation |
| CN111399098A (en) * | 2019-06-05 | 2020-07-10 | 江西师范大学 | Sunlight anti-reflector and preparation method thereof |
| CN112086387B (en) * | 2020-08-14 | 2021-06-04 | 北京智创芯源科技有限公司 | Chip cleaning device and cleaning method |
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