CN101876725A - Method for forming substrate with periodic structure - Google Patents
Method for forming substrate with periodic structure Download PDFInfo
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- CN101876725A CN101876725A CN2009101379052A CN200910137905A CN101876725A CN 101876725 A CN101876725 A CN 101876725A CN 2009101379052 A CN2009101379052 A CN 2009101379052A CN 200910137905 A CN200910137905 A CN 200910137905A CN 101876725 A CN101876725 A CN 101876725A
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Abstract
The invention relates to a method for forming a substrate with a periodic structure, comprising the following steps: (A) providing a substrate and a plurality of nanospheres which are arranged on the surface of the substrate; (B) forming one layer on parts of surface of the substrate and the gap of the nanospheres; (C) removing a plurality of nanospheres; (D) causing a packing layer to serve as etch shield, and etching the substrate; and (E) removing the etch shield so as to form the periodic structure on the surface of the substrate. Because of using the nanosphere to serve as the template of the etch shield, the invention can quicken technology without yellow light photoetching technology and achieve the purpose of lowering manufacturing cost.
Description
Technical field
The present invention relates to a kind of formation one and have the method for periodic structure substrate, refer to especially a kind of can quick Fabrication, with low cost and can avoid the formation one of substrate damage to have the method for periodic structure substrate.
Background technology
So-called photonic crystal is a kind of periodic structure, can make the light of some frequency be confined to a specific direction propagation, and can prevent the propagation of the light of other frequency; And because of its opereating specification of photonic crystal is the scope of light, so the structural cycle size of photonic crystal is necessary for time micron or nano-scale.At present, photonic crystal also can be with photonic crystal applications in the usefulness of photovalve with the enhancement photovalve except that can be applicable to fields such as optical communication system and light counter.
Generally be with mode patterned substrates such as moulding of high-energy engraving or nano impression arts forming photonic crystal, as laser, electron beam, ion beam chisel and carve moulding, the laser full figure is interfered or make behind the hard photonic crystal motherboard again with the technology of motherboard inscription rubbing in soft base material with said method.Yet the moulding of high-energy engraving has the shortcoming of high cost and low production capacity, though and the cost of nano impression art higher-energy engraving moulding is low and production capacity is higher, but still can't satisfy the demand of low-cost and high production capacity.
At present, can adopt dry ecthing or wet etch process patterned substrate, have the substrate of periodic structure with formation.With the dry ecthing method is example, shown in Figure 1A to Fig. 1 F.At first, shown in Figure 1A, provide a substrate 10; Then form a photoresist layer 11, shown in Figure 1B in substrate 10 surfaces 101.Then, on photoresist layer 11, cover a light shield 12, and expose, shown in Fig. 1 C with patterning photoresist layer 11.After development and removing light shield 12, can get a patterned light blockage layer 11, shown in Fig. 1 D.Then, as an etch shield, utilize reactive ion gas etch substrate 10 with patterned light blockage layer 11, to form a plurality of nicks cave 102, shown in Fig. 1 E.Then, remove patterned light blockage layer 11 (etch shield) after, can get the substrate 10 of a patterning, shown in Fig. 1 F.Wherein, substrate 10 its surfaces 101 of this patterning have the periodic structure of being arranged formation with a plurality of nicks cave 102.
Yet though can produce the substrate of the neat and uniform tool periodic structure of figure with above-mentioned dry ecthing method, the shortcoming of right the method is: because of carrying out the gold-tinted photoetching process, so cost is high and product is fast low; If will form the nanometer-scale periodic structure, then adopts sub-micron light cover costliness, and as want below the 500nm figure then cost improve more; Reactive ion gas etch board costliness and technology are slow; The easy damaged substrate; And the non-natural lattice plane of etching face.
Form substrate for solving the problem of dry ecthing method, develop at present with periodic structure with wet etch method; Shown in Fig. 2 A to Fig. 2 F, being with＜100〉monocrystalline silicon substrate in crystal orientation is example.Wherein, forming and to have the method for periodic structure substrate, is similar to dry ecthing method, except with buffering etching solution etching substrates.Therefore, shown in Fig. 2 A to 2D, form patterned light blockage layer 11 (seeing also Fig. 2 D) with exposure imaging method (photoetching process) earlier; Then with patterned light blockage layer 11 as an etch shield, with anisotropic buffering etching solution etching substrates 10, to form a plurality of nicks cave 102, shown in Fig. 2 E.Then, remove patterned light blockage layer 11 (etch shield) after, can get the substrate 10 of a patterning, shown in Fig. 2 F.Wherein, substrate 10 its surfaces 101 of this patterning have the periodic structure of being arranged formation with a plurality of nicks cave 102.It should be noted that it is shaped as down quadrangular pyramid with wet etching patterned substrate 10 formed nick caves 102, this fall quadrangular pyramid around the inclined-plane, also be monocrystalline silicon＜111〉natural lattice plane.
Though can avoid substrate to sustain damage and etching face is the nature lattice plane with the wet etch method patterned substrate; Yet, if parameter control is improper, can cause the homogeneity of periodic structure relatively poor when carrying out wet etching.Simultaneously because of still carrying out photoetching process in the above-mentioned manufacturing process, so still face the cost height and produce problems such as speed is low.
Therefore, need the method that develops a kind of patterned substrate at present badly, sustain damage except avoiding substrate, and can be fast and cheap formation have the periodic structure substrate.
Summary of the invention
Fundamental purpose of the present invention is to provide a kind of formation one to have the method for periodic structure substrate, can reduce the process time, reduces cost of manufacture, also can avoid substrate to sustain damage simultaneously.
For reaching above-mentioned purpose, the present invention's formation has the method for periodic structure substrate, comprises the following steps: that (A) provides a substrate and a plurality of nanosphere, and wherein a plurality of nanospheres are arranged in the surface of this substrate; (B) form a packed layer in the gap of part surface and a plurality of nanospheres of substrate; (C) remove a plurality of nanospheres; (D) with packed layer as an etch shield and etching substrates; And (E) remove etch shield, to form the one-period structure in the surface of substrate.
The present invention is a self assembly characteristic of utilizing nanosphere, and promptly these nanospheres can be automatically and are arranged in the surface of a substrate in an orderly manner, replace the gold-tinted photoetching process, to form the template of etch shield.Simultaneously, utilize the nanosphere of these auto arrangement, because of not making expensive time micron exposure shielding, so the periodic structure that cost that can be cheaper forms.Therefore, formation of the present invention has the method for periodic structure substrate, can reach the purpose that reduces the process time, reduces cost of manufacture; And material required for the present invention also is very easy to obtain, so quite be fit to a large amount of substrates that form periodic structure.
Have in the method for periodic structure substrate in formation of the present invention, the periodic structure of substrate surface has a plurality of nicks cave.Be preferably, a plurality of nicks cave is in array-like arrangement.In addition, the shape in nick cave is centered on by the natural lattice plane that produces in the etching substrates process to form, and can be chamfering awl, inverted cone, right cylinder, the pyramid of falling the butt, the frustum of a cone that falls.The substrate of unlike material and different etching solutions can produce difform nick cave.As be that aforesaid monocrystalline silicon substrate adopts the NaOH etching, then the nick cave is one to fall quadrangular pyramid, wherein the bottom of quadrangular pyramid is positioned at substrate surface, and the top of quadrangular pyramid is to cave in from substrate surface.If with hydrofluoric acid etch liquid corrosion carved glass substrate, then being shaped as of nick cave one fallen frustum of a cone.
Have in the method for periodic structure substrate in formation of the present invention, also comprise a step (F) after the step (E): this substrate surface of etching again.In the substrate of the formed tool periodic structure of step (E), for having a plane, and can be considered a notch board structure between wherein adjacent nick cave.And, then increase the width and the degree of depth in nick cave if pass through step (F) etching again again, do not have a plane between adjacent nick cave and make, and can be considered a flange structure.
Have in the method for periodic structure substrate in formation of the present invention, formed periodic structure can be nanoscale or micron-sized periodic structure; Wherein, periodic structure is preferably the periodic structure of nanoscale or sub-micron grade, and is more preferred from the nanoscale periodic structure.Have in the method for periodic structure substrate in formation of the present invention, a plurality of nanospheres of step (A) are arranged in the step of substrate surface, comprise the following steps: that (A1) provides substrate, an and colloidal solution that is arranged in a container, and colloidal solution comprises a plurality of nanospheres and an interface activating agent; (A2) place substrate in container, and colloidal solution is covered in the surface of substrate; And (A3) add the volatile solution of a tool in container, increasing solution evaporation speed, and impel a plurality of nanospheres to arrange in the surface of substrate.Wherein, a plurality of nanospheres form a nanosphere layer, and are preferably the nanosphere layer of one deck.
Have in the method for periodic structure substrate in formation of the present invention, the method for the etching substrates of step (D) can be dry ecthing method or wet etch method, is preferably wet etch method.Wherein, wet etch method is with a buffering etching solution etching substrates, and the buffering etching solution can be material selection general acidity or alkaline etching liquid commonly used according to substrate and packed layer.Wherein, acidic etching liquid can comprise an acid solution, an alcohols and water, and alkaline etching liquid then comprises an alkali lye, an alcohols and water.Acid solution is preferably hydrofluorite, BOE (HF and NH
4The F mixed solution), hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid or its mixed solution.Perhaps, acid solution also can be for by monoethanolamine (ethanolamine), gallic acid (gallic acid), water, hydrogen peroxide (hydrogen peroxide), and Amine Callates that surfactant mixed.In addition, alkali lye is preferably NaOH, potassium hydroxide, ammoniacal liquor, cerium hydroxide, rubidium hydroxide, tetramethylammonium hydroxide, ethylenediamine or diamine.Moreover alcohols is preferably ethanol or isopropyl alcohol.Use the wet etch method etching substrates because method of the present invention is preferably, therefore can reach the purpose of avoiding substrate damage.
Have in the method for periodic structure substrate in formation of the present invention, the material of nanosphere there is no particular restriction, is preferably monox (SiO
x), pottery, polymethylmethacrylate (PMMA), titanium dioxide (TiO
x) or polystyrene (PS).In addition, the diameter of nanosphere can be preferably between 100nm to 1.2 μ m between 100nm to 2.5 μ m, and a plurality of nanosphere is preferably and has identical diameter.
Have in the method for periodic structure substrate in formation of the present invention, the method of the formation packed layer of step (B) there is no particular restriction, be preferably and utilize chemical vapour deposition technique or physical vaporous deposition, to form packed layer in the part surface of substrate and the gap of a plurality of nanospheres.In addition, the thickness of packed layer is to decide according to the nick cave size that institute's desire forms, and is preferably the diameter less than these a plurality of nanospheres.Moreover the material of packed layer there is no particular restriction, can be general material as etch shield commonly used; And be preferably monox, silicon nitride, silicon oxynitride, aluminium oxide, zinc paste, tin indium oxide, doped zinc oxide aluminium, chromium, tantalum, tungsten, vanadium, nickel, tin, iron, copper, molybdenum, titanium, aluminium, silver, gold, platinum, palladium or photoresistance (PR), polymethylmethacrylate (PMMA), polystyrene (PS).
Have in the method for periodic structure substrate in formation of the present invention, the material of substrate there is no particular restriction, can do selection according to applied field.Wherein, substrate material can be p type single crystal silicon, n type single crystal silicon, P type polysilicon, N type polysilicon, P type amorphous silicon, N type amorphous silicon, P p type gallium arensidep, N p type gallium arensidep, p type inp, n type inp, P type InGaP, N type InGaP, P type gallium nitride, n type gallium nitride, P type copper indium diselenide, N type copper indium diselenide, tin indium oxide, silit, silicon nitride, quartz or zinc paste and doped zinc oxide aluminium compound.Perhaps, the employed substrate of method of the present invention also can be sapphire substrate (signle crystal alumina).Be preferably, the employed substrate of method of the present invention is P type silicon substrate or sapphire substrate.
In addition, the employed substrate of method of the present invention also can be the glass substrate that glass substrate or surface have nesa coating (TCO) layer.If the substrate that uses has the glass substrate of nesa coating (TCO) layer as the surface, then periodic structure is for being formed on nesa coating (TCO) layer; Otherwise also can.
Formation of the present invention has the method for periodic structure substrate, except utilizing the template of nanosphere, to replace the gold-tinted photoetching process, simultaneously as etch shield, also utilize the Wet-type etching patterned substrate, so can reach uniform periodic structure and avoid the purpose of substrate damage.Therefore, formation of the present invention has the method for periodic structure substrate, can be simply, cost is low, and the mode patterned substrate of high production capacity.
Description of drawings
Figure 1A to Fig. 1 F is existing diagrammatic cross-section of making the flow process with periodic structure substrate with dry ecthing method.
Fig. 2 A to Fig. 2 F is existing diagrammatic cross-section of making the flow process with periodic structure substrate with the anisotropic wet etch method.
Fig. 3 A to Fig. 3 F is in a preferred embodiment of the present invention, and nanosphere is arranged in the step synoptic diagram of substrate surface.
Fig. 4 A to Fig. 4 E is in a preferred embodiment of the present invention, forms to have the diagrammatic cross-section of periodic structure substrate.
Fig. 5 A is in a preferred embodiment of the present invention, and nanosphere is arranged in the SEM figure of monocrystalline silicon substrate.
Fig. 5 B is the SEM figure of the monocrystalline silicon substrate with periodic structure of a preferred embodiment of the present invention.
Fig. 6 is the synoptic diagram with periodic structure substrate of a preferred embodiment of the present invention.
Fig. 7 be another preferred embodiment of the present invention have a periodic structure substrate synoptic diagram.
Fig. 8 be the present invention again a preferred embodiment have a periodic structure substrate synoptic diagram.
Fig. 9 be a preferred embodiment of the present invention have a periodic structure substrate synoptic diagram.
[main element symbol description]
10 substrates, 101 surfaces
102 nick caves, 11 photoresist layers
12 light shields, 201 surfaces
202 nick caves, 21 substrates
22 nanospheres, 23 packed layers
24 etch shield, 25 colloidal solution
26 containers, 27 volatile solvent solns
Embodiment
Shown in Fig. 3 A to Fig. 3 F, this is in a preferred embodiment of the present invention, and nanosphere is arranged in the step synoptic diagram of substrate surface.At first, as shown in Figure 3A, the colloidal solution 25 that provides a substrate 21 and to be arranged in a container 26, wherein this colloidal solution 25 is to be mixed by a plurality of nanosphere (not shown) and an interfacial agent (not shown).Then, be positioned over this substrate 21 in the container 26 and make substrate 21 be immersed in fully in the colloidal solution 25, shown in Fig. 3 B.After leaving standstill several minutes,, promptly form so-called " nanosphere layer ", shown in Fig. 3 C just nanosphere 22 is arranged in substrate 21 surfaces gradually in an orderly manner.Then, a volatile solvent soln 27 is poured in the container 26, so that aforesaid colloidal solution 25 is vapored away, shown in Fig. 3 D.At last, shown in Fig. 3 E, wait until that aforesaid colloidal solution 25 is volatilized fully after, have a plurality of nanospheres 22 and be arranged in its surperficial substrate 21 in an orderly manner just substrate 21 taken out from container 26 and obtain one, as Fig. 3 F.
In present embodiment, the material of nanosphere 22 is polystyrene (PS), but in different application scenarios, and the material of these nanospheres 22 also can be pottery, as titanium dioxide (TiO
x) metal oxide, polymethylmethacrylate (PMMA) or glass (SiO
x) etc. material.In addition, in present embodiment, the diameter of nanosphere 22 is between 100nm to 2.5 μ m, and most nanosphere 22 has identical diameter, but when different application scenarios, the size of these nanospheres 22 is not limited only to aforesaid scope.
In addition, in present embodiment, the material of substrate is a monocrystalline silicon substrate.Yet, the material of substrate is to elect according to different application scenarios, can be p type single crystal silicon, n type single crystal silicon, P type polysilicon, N type polysilicon, P type amorphous silicon, N type amorphous silicon, P p type gallium arensidep, N p type gallium arensidep, p type inp, n type inp, P type InGaP, N type InGaP, P type gallium nitride, n type gallium nitride, P type copper indium diselenide, N type copper indium diselenide, tin indium oxide, silit, silicon nitride, quartz or zinc paste and doped zinc oxide aluminium compound; And also can be the glass substrate that sapphire substrate (signle crystal alumina), glass substrate, surface have nesa coating (TCO) layer.
Next, see also Fig. 4 A to Fig. 4 E, this is in a preferred embodiment of the present invention, forms to have the diagrammatic cross-section of periodic structure substrate.In addition, and simultaneously with reference to figure 5A to Fig. 5 B, this is in a preferred embodiment of the present invention, forms the SEM figure with periodic structure substrate.
At first, shown in Fig. 4 A, provide a substrate 21 and a plurality of nanosphere 22, and, make a plurality of nanospheres 22 be arranged in the surface of substrate 21, and form a nanosphere layer according to above-mentioned method.Wherein, nanosphere 22 can multiple-level stack in substrate 21 surfaces, and in present embodiment, nanosphere 22 is that the mode with one deck is arranged in substrate 21 surfaces.Show that by the SEM of Fig. 5 A figure the mode that nanosphere really can one deck is arranged in the surface of substrate.
Then, shown in Fig. 4 B, utilize chemical vapour deposition technique to form the gap of a packed layer 23 in part surface and a plurality of nanosphere 22 of substrate 21.Wherein, the thickness of packed layer 23 is less than the diameter of these a plurality of nanospheres, and the material of packed layer is a silicon nitride.Yet, except forming the packed layer 23 by chemical vapour deposition technique, can also form by physical vaporous deposition, and the material of packed layer 23 also can be other and is usually used in metal as etch shield, as monox, silicon oxynitride, aluminium oxide, zinc paste, tin indium oxide, doped zinc oxide aluminium, chromium, tantalum, tungsten, vanadium, nickel, tin, iron, copper, molybdenum, titanium, aluminium, silver, gold, platinum, palladium or photoresistance (PR), polymethylmethacrylate (PMMA), polystyrene (PS).
Then, use the tetrahydrochysene Fu solution (THF) of muttering to remove a plurality of nanospheres 22, and with packed layer 23 as an etch shield 24, shown in Fig. 4 C.In this attention is that the nanosphere of unlike material need use different solution these nanospheres could be removed from substrate.For instance, if use the nanosphere of polymethylmethacrylate (PMMA) material, then be to use formic acid (formic acid) to remove nanosphere; If use glass (SiO
x) nanosphere of material, then be the hydrofluoric acid containing of using (HF) solution remove nanosphere.
Then, shown in Fig. 4 D, with packed layer as an etch shield 24, with wet etch method etching substrates 21.In present embodiment, the employed buffering etching solution of wet etch method comprises NaOH, isopropyl alcohol and water.Yet, according to the material of substrate and packed layer, also can select different buffering etching solutions, as alkalescence buffering etching solution or acidic buffer etching solution.In alkalescence buffering etching solution, can comprise: as alkali lye such as NaOH, potassium hydroxide, ammoniacal liquor, cerium hydroxide, rubidium hydroxide, tetramethylammonium hydroxide, ethylenediamine or diamines; As alcohols such as ethanol or isopropyl alcohols; And water.And in the acidic buffer etching solution, can comprise: as acid solution is hydrofluorite, BOE (HF and NH
4The F mixed solution), hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid or its mixed solution.Perhaps, acid solution also can be for by monoethanolamine (ethanolamine), gallic acid (gallic acid), water, hydrogen peroxide (hydrogen peroxide), and Amine Callates that surfactant mixed; And as alcohols such as ethanol or isopropyl alcohols; And water.In addition, can be by adjusting composition and concentration, etch temperature and the time of buffering etching solution, to obtain different etch structures.Simultaneously, along with etch temperature rises, the required time with minimizing.
After removing etch shield 24, can form a plurality of nicks cave 202 in substrate 21 surfaces 201, promptly so-called " periodic structure " is shown in Fig. 4 E.Wherein, these nick caves 202 are in array-like arrangement, and because of the material of substrate 21 is a monocrystalline silicon substrate, etching solution is NaOH, isopropyl alcohol and water, so formed nick cave 202 be shaped as down quadrangular pyramid, the bottom that is quadrangular pyramid is positioned at substrate 21 surfaces 201, and the top of quadrangular pyramid is from substrate 21 surfaces 201 depressions.Simultaneously, please refer to Fig. 5 B, this is for after etching and removing etch shield, and the SEM with periodic structure substrate of gained schemes.Can learn clearly that by Fig. 5 B the profile in its nick cave of the prepared substrate of present embodiment is the shape of falling the quadrangular pyramid really.
For the clear more periodic structure of understanding on the prepared substrate surface of present embodiment, please refer to Fig. 6, this is the synoptic diagram with periodic structure substrate of a preferred embodiment of the present invention.Utilize that said method is formed to have a periodic structure substrate, be formed with a plurality of nicks cave 202 of arranging in substrate 21 surfaces 201 with array-like, and this slightly depression 202 be shaped as down quadrangular pyramid (inverted pyramid shape).
The foregoing description is to use monocrystalline silicon substrate, so can form the nick cave that is shaped as down quadrangular pyramid, its reason is that the shape in nick cave is centered on by the natural lattice plane that produces in the etching substrates process to form.The substrate of unlike material and different etching solutions can produce difform nick cave.
Next, another preferred embodiment of the present invention is to use above-mentioned identical method for making to make, and replaces monocrystalline silicon substrate except using sapphire substrate, and wherein, etching solution is to use sulfuric acid, phosphoric acid mixed solution.After etching, can form pyramid nick cave, as shown in Figure 7.Wherein, 202 in adjacent nick cave has a surface 201, and the plane is positioned on the sustained height.At this, can make the sapphire substrate with periodic structure of notch board.After SEM measured, the length of pyramid top in the subpoint of bottom to the base was about 310nm, and the length of pyramid is about 410nm.So prepared its periodic structure of notch board sapphire substrate of present embodiment is the nanoscale periodic structure.
In addition, the present invention more provides a preferred embodiment again, and it is with the prepared sapphire substrate of another preferred embodiment of the present invention, carries out etching again, to highlight the thick behaviour's degree in sapphire substrate surface.After the etching second time, scope expansion, the degree of depth in nick cave 202 can be deepened, also eliminate by etching on 202 planes, adjacent nick cave.So 202 adjacent in nick cave then no longer has a plane, therefore, and can make the sapphire substrate with periodic structure of flange, as shown in Figure 8.
Moreover a more preferred embodiment of the present invention is to use above-mentioned identical method for making to make, and replaces monocrystalline silicon substrate except using glass substrate.Wherein, etching solution is to use hydrofluoric acid solution, because of hydrofluoric acid etch liquid itself is isotropic etching, thus can form the nick cave 202 that is shaped as down truncated cone, as shown in Figure 9.
Added compared to use gold-tinted to develop in the past that wet etch method forms the silicon substrate of tool periodic structure, can't reach nano level size.Though use dry ecthing method can form the nano-grade size periodic structure, yet spend suitable costliness and technology is quite complicated, a slice is asked a price about 300,000 yuan.In addition, the sapphire substrate with existing method making tool periodic structure often can't form the nano-grade size periodic structure.Reviewing and of the present inventionly have the substrate of periodic structure with nanosphere preparation, is the characteristic of utilizing the nanosphere self assembly, but and proper alignment in the surface of substrate.Simultaneously, by selecting the nanosphere of different-diameter, can form substrate easily, to be applied to different field with virtually any size nick cave; And by selecting the nanosphere of tool nano-scale for use, and can reach the tool nanosized microstructure easily.In addition, compared to formed periodic structure with beamwriter lithography in the past, method of the present invention can significantly reduce cost of manufacture; And compared to formed etch shield with gold-tinted photoetching process (exposure and development) in the past, because the present invention is arranged the nanosphere layer that the forms template as the formation etch shield with nanosphere, and need not use time micron exposure shielding, so can significantly reduce cost of manufacture and promote process speed.Moreover compared to the employed RIE of dry ecthing or ICP board costliness and high-risk, the present invention is to use the lower and dangerous low wet corrosion cutting of price to carry out wet etching; And compared to the dry ecthing method of easy damaged substrate, the present invention uses wet etch method to form periodic structure, can avoid substrate to sustain damage.Therefore, by method of the present invention, can be fast and inexpensive manner, form substrate with periodic structure.
The foregoing description only is to give an example for convenience of description, and the interest field that the present invention advocated should be as the criterion so that claim is described certainly, but not only limits to the foregoing description.
Claims (23)
1. a formation one has the method for periodic structure substrate, it is characterized in that, comprises the following steps:
(A) provide a substrate and a plurality of nanosphere, wherein these a plurality of nanospheres are arranged in the surface of this substrate;
(B) form a packed layer in the gap of part surface and these a plurality of nanospheres of this substrate;
(C) remove this a plurality of nanospheres;
(D) with this packed layer as an etch shield and this substrate of etching; And
(E) remove this etch shield, to form the one-period structure in the surface of this substrate.
2. the method for claim 1 is characterized in that, also comprises a step (F) after the step (E): this substrate surface of etching again.
3. the method for claim 1 is characterized in that, wherein this periodic structure is the nanoscale periodic structure.
4. the method for claim 1 is characterized in that, wherein these a plurality of nanospheres of step (A) are arranged in the surface of this substrate, comprising:
(A1) provide this substrate, an and colloidal solution that is arranged in a container, and this colloidal solution comprises these a plurality of nanospheres and an interface activating agent;
(A2) place this substrate in this container, and this colloidal solution is covered in the surface of this substrate; And
(A3) add the volatile solution of a tool in container,, and impel a plurality of nanospheres to arrange in the surface of substrate with increase solution evaporation speed.
5. the method for claim 1 is characterized in that, wherein this packed layer is to utilize chemical vapour deposition technique or physical vaporous deposition to be formed at the gap of part surface and these a plurality of nanospheres of this substrate.
6. the method for claim 1 is characterized in that, wherein step (D) is with this substrate of buffering etching solution etching.
7. method as claimed in claim 6 is characterized in that, wherein this buffering etching solution comprises an alkali lye, an alcohols and water.
8. method as claimed in claim 6 is characterized in that, wherein this buffering etching solution comprises an acid solution, an alcohols and water.
9. method as claimed in claim 7 is characterized in that, wherein this alkali lye is NaOH, potassium hydroxide, ammoniacal liquor, cerium hydroxide, rubidium hydroxide, tetramethylammonium hydroxide, ethylenediamine or diamine.
10. method as claimed in claim 7 is characterized in that, wherein this alcohols is ethanol or isopropyl alcohol.
11. method as claimed in claim 8 is characterized in that, wherein this acid solution is hydrofluorite, BOE (HF and NH
4The F mixed solution), hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid or its mixed solution.Perhaps, acid solution also can be for by monoethanolamine (ethanolamine), gallic acid (gallic acid), water, hydrogen peroxide (hydrogen peroxide), and Amine Callates that surfactant mixed.
12. method as claimed in claim 8 is characterized in that, wherein this alcohols is ethanol or isopropyl alcohol.
13. the method for claim 1 is characterized in that, wherein this periodic structure in the surface of this substrate has a plurality of nicks cave.
14. method as claimed in claim 13 is characterized in that, wherein this a plurality of nicks cave is in array-like arrangement.
15. method as claimed in claim 14 is characterized in that, wherein this a plurality of nicks cave is shaped as chamfering awl, inverted cone, right cylinder, the pyramid of falling the butt, falls frustum of a cone.
16. the method for claim 1, it is characterized in that wherein the material of this substrate is p type single crystal silicon, n type single crystal silicon, P type polysilicon, N type polysilicon, P type amorphous silicon, N type amorphous silicon, P p type gallium arensidep, N p type gallium arensidep, p type inp, n type inp, P type InGaP, N type InGaP, P type gallium nitride, n type gallium nitride, P type copper indium diselenide, N type copper indium diselenide, tin indium oxide, silit, silicon nitride, quartz, zinc paste and doped zinc oxide aluminium compound.
17. the method for claim 1 is characterized in that, wherein this substrate is a sapphire substrate.
18. the method for claim 1 is characterized in that, wherein this substrate is the glass substrate that a glass substrate or a surface have nesa coating (TCO) layer.
19. the method for claim 1, it is characterized in that wherein the material of this packed layer is monox, silicon nitride, silicon oxynitride, aluminium oxide, zinc paste, tin indium oxide, doped zinc oxide aluminium, chromium, tantalum, tungsten, vanadium, nickel, tin, iron, copper, molybdenum, titanium, aluminium, silver, gold, platinum, palladium or photoresistance (PR), polymethylmethacrylate (PMMA), polystyrene (PS).
20. the method for claim 1 is characterized in that, wherein the material of this nanosphere is monox, pottery, polymethylmethacrylate, titanium dioxide or polystyrene.
21. the method for claim 1 is characterized in that, wherein the thickness of this packed layer is less than the diameter of these a plurality of nanospheres.
22. the method for claim 1 is characterized in that, wherein the diameter of these a plurality of nanospheres is between 100nm to 2.5 μ m.
23. the method for claim 1 is characterized in that, wherein these a plurality of nanospheres have identical diameter.
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| CN102709156A (en) * | 2012-05-25 | 2012-10-03 | 中山大学 | Wet etching method for ZnO-based transparent conductive film |
| CN102779747A (en) * | 2012-07-30 | 2012-11-14 | 江苏物联网研究发展中心 | Machining method of nano column/needle forest structure |
| CN103803618A (en) * | 2013-12-30 | 2014-05-21 | 中国科学院宁波材料技术与工程研究所 | Preparation method of three-dimensional nano structure of porous anodic aluminum oxide |
| CN103825103A (en) * | 2014-03-10 | 2014-05-28 | 西南科技大学 | Method for constructing broadband metamaterial based on various dielectric spheres |
| CN103901513A (en) * | 2014-04-21 | 2014-07-02 | 山东大学 | Photonic crystal of two-dimensional graphene-like duplex structure |
| TWI476144B (en) * | 2012-05-14 | 2015-03-11 | Univ Nat Taiwan | Method for preparing a periodic nanohole structure array and the use thereof |
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| TWI476144B (en) * | 2012-05-14 | 2015-03-11 | Univ Nat Taiwan | Method for preparing a periodic nanohole structure array and the use thereof |
| CN102709156A (en) * | 2012-05-25 | 2012-10-03 | 中山大学 | Wet etching method for ZnO-based transparent conductive film |
| CN102709156B (en) * | 2012-05-25 | 2016-09-07 | 中山大学 | A kind of ZnO-based transparent conductive film wet etching method |
| CN102779747A (en) * | 2012-07-30 | 2012-11-14 | 江苏物联网研究发展中心 | Machining method of nano column/needle forest structure |
| CN102779747B (en) * | 2012-07-30 | 2014-11-05 | 江苏物联网研究发展中心 | Machining method of nano column/needle forest structure |
| CN103803618A (en) * | 2013-12-30 | 2014-05-21 | 中国科学院宁波材料技术与工程研究所 | Preparation method of three-dimensional nano structure of porous anodic aluminum oxide |
| CN103803618B (en) * | 2013-12-30 | 2016-03-16 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of porous anodic aluminium oxide 3-D nano, structure |
| CN103825103A (en) * | 2014-03-10 | 2014-05-28 | 西南科技大学 | Method for constructing broadband metamaterial based on various dielectric spheres |
| CN103901513A (en) * | 2014-04-21 | 2014-07-02 | 山东大学 | Photonic crystal of two-dimensional graphene-like duplex structure |
| CN108878262A (en) * | 2018-06-12 | 2018-11-23 | 重庆中科渝芯电子有限公司 | A kind of highly doped Si substrate devices bottom SI quantifies minimizing technology |
| CN110857748A (en) * | 2018-08-24 | 2020-03-03 | 王磊 | Interface material layer and manufacturing method thereof |
| CN109655971A (en) * | 2018-11-14 | 2019-04-19 | 华南师范大学 | A method of micro-nano structure is prepared on planar optical waveguide surface |
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