CN101497429A - Method for preparing silicon hollow nano-cone array - Google Patents
Method for preparing silicon hollow nano-cone array Download PDFInfo
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Abstract
The invention relates to a method for preparing a hollow silicon nano conical array, in particular to a method for preparing the hollow silicon nano conical array with large area, uniform bottom diameter length, controllable spacing, controllable period and orderly arrangement. The method comprises the following four steps: washing and surface hydrophilization treatment of a monocrystalline silicon piece, preparation of polystyrene monolayer colloidal crystals, preparation of a hollow silicon nano column array, and construction of a hollow silicon nano conical array. The hollow silicon nano conical array obtained by the method has the advantages of large area, uniform bottom diameter length, controllable spacing, controllable period and orderly arrangement, has extremely superior broad-band dereflection performance, and effectively reduces the surface reflection loss from deep ultraviolet band to medium infrared band (250 nanometers to 15 mu m). The method is simple and controllable, and has wide application prospect on construction of photoelectric devices with low cost and large area and deflection surfaces.
Description
Technical field
The present invention relates to a kind of preparation method of silicon hollow nano-cone array, the preparation method of the silicon hollow nano-cone array of relate to particularly that large tracts of land, end electrical path length homogeneous, spacing are controlled, controlling cycle, arrangement are orderly.
Background technology
Silicon is most important material in the current semi-conductor industry, because the asymmetry of silicon nanocone shape and pointed top, its array is had widely use, for example be applied to antireflection coatings, efficient feds, high sensor, self-cleaning surface etc.
The method of existing preparation silicon nano-cone array probably has three kinds: chemical gaseous phase depositing process, laser ablation methods, lithographic method.Preceding two kinds of method length consuming time, be difficult to performance period spacing controlled, be difficult to realize constructing of large tracts of land array.Electron beam (E-Beam) etching, FIB (FIB) etching can be controlled parameters such as the cycle, footpath, the end of silicon nano-cone array accurately, but the expensive cost height of employed instrument, and the efficient of E-Beam etching and FIB etching is very low, is difficult to realize large-area constructing.Reactive ion etching (RIE) cost is cheap relatively, is easy to realize large-area constructing, but is difficult to realize the constructing of silicon nano-cone array of high length-diameter ratio.An important application of silicon nano-cone array is to be used to construct antireflection coatings.Reduce the reflection of light on the surface, have important effect in actual applications, have the solar cell that the substrate of antireflection coatings is constructed as utilization, its efficient is higher than traditional thin-film solar cells.
Summary of the invention
The object of the present invention is to provide the preparation method of silicon hollow nano-cone array of the orderly arrangement of a kind of large tracts of land, controlling cycle.
Purpose of the present invention can be achieved through the following technical solutions: utilize non-closelypacked colloidal crystal template assistant metal catalysis etch silicon technology to obtain the silicon nano column array of vertical hollow, binding reactive ion etching again (RIE) obtains the silicon nano-cone array of hollow.
This method technology is simple, cost is low, particularly electrical path length homogeneous at the bottom of Zhi Bei the nano-cone array, draw ratio height (can reach 12), arrange in order, even can compare favourably with the silicon nano-cone array that expensive process such as electron beam lithography, focused-ion-beam lithography are prepared.
Method of the present invention comprises four steps:
1. the cleaning of monocrystalline silicon piece and surface hydrophilic are handled: silicon chip passes through the acetone ultrasonic cleaning successively 10～15 minutes, absolute ethyl alcohol ultrasonic cleaning 10～15 minutes, oven dry, the acidic treatment liquid (mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide, the consumption volume ratio of two kinds of solution is 7:3) boil and handled 20～30 minutes, through dry under nitrogen or air atmosphere after the rinsed with deionized water, obtain the monocrystalline silicon piece substrate of cleaning surfaces and hydrophilicity-imparting treatment again;
2. the preparation of polystyrene colloid monolayer crystalline substrate: with the size range of dispersin polymerization preparation is that (preparation method of polystyrene microsphere is referring to J.H.Zhang for the polystyrene microsphere of 300～1000 nanometers, Z.Chen, Z.L.Wang, W.Y.Zhang, N.B.Ming, Mater.Lett.2003,57,4466.) after the eccentric cleaning, be that absolute ethyl alcohol and the deionized water mixed solution of 1～2.5:1 disperses with volume ratio, obtain mass percentage concentration and be 0.5～2.0% emulsion; Be added drop-wise to slowly on the glass culture dish that fills deionized water with the emulsion of syringe again, drip 20～50 microlitre mass percent concentrations again and be 2.0～8.0% sodium dodecyl sulfate solution the above-mentioned concentration of 50～100 microlitres; With the monocrystalline silicon piece substrate polystyrene individual layer of keeping afloat is picked up, after the air dry, just obtained the polystyrene colloid crystalline substrate of individual layer;
3. constructing of hollow silicon nano column array: closelypacked polystyrene colloid crystal is become non-closelypacked colloidal crystal with reactive ion etching, etching power is RF20～40W, ICP200～400W, chamber pressure is 5～15mTorr, oxygen flow is 40～60SCCM, etch period is 30～75 seconds, then substrate is heated 10～15 minutes in 120～150 ℃ of baking ovens; In substrate, deposit the thick silverskin of 35～55nm again, (hydrofluoric acid concentration is 2.0～5.0mol/L afterwards substrate to be immersed the mixed solution of hydrofluoric acid and hydrogen peroxide, the concentration of hydrogen peroxide is 0.20～0.45mol/L,) the middle processing 6～30 minutes, use the chloroazotic acid (mixed solution of concentrated hydrochloric acid and red fuming nitric acid (RFNA) more successively, volume ratio is 3:1) remove silverskin, remove polystyrene microsphere with chloroform, promptly obtain the silicon nano column array of hollow;
4. constructing of hollow silicon nano-cone array: the reactive ion etching that the hollow silicon nano column array that obtains is carried out fluorine, etching power is RF50～150W, ICP400～600W, chamber pressure is 5～15mTorr, the fluoroform flow is 20～40SCCM, the sulfur hexafluoride flow is 4～8SCCM, and etch period is 60～210 seconds, obtains hollow silicon nano-cone array at last, cycle is adjustable to 800 nanometers from 250 nanometers, and height is adjustable to 7.1 microns from 2.0 microns.
Utilize the hollow silicon nano-cone array of method for preparing,, make the effective refractive index of silicon nanocone increase progressively to tang portion, thereby formed the refractive index of gradient gradual change from cone top part because it has the profile of taper.According to theoretical proof,, will reduce the reflection loss that the difference owing to the two media refractive index causes if on the two media interface, there is the coating of the graded of effective refractive index.The reflection loss that reduces the surface in actual applications is crucial, for example: utilize the substrate with antireflection coatings to construct the efficient that solar cell can improve solar cell significantly; On optical lens, construct antireflection coatings and can improve the transmitance of light, improve the performance of optics; If on the substrate of glass of light emitting diode, construct antireflection coatings, can improve the light extraction efficiency of light emitting diode, and then improve the efficient of light emitting diode.In addition, silicon hollow nano-cone array is owing to having pointed end, so it has potential application on feds.
Description of drawings
Fig. 1: the schematic diagram of preparation hollow silicon nano-cone array;
Wherein steps A is the closelypacked polystyrene two-dimensional colloidal crystal of preparation on monocrystal silicon substrate; Step B is that reactive ion etching prepares non-closelypacked polystyrene two-dimensional colloidal crystal; Step C is at non-closelypacked polystyrene two-dimensional colloidal crystal evaporation silverskin; Step D is a preparation silicon hollow nano column array; Step e is that the fluorine reactive ion etching prepares hollow silicon nano-cone array.1 represents polystyrene microsphere, and 2 represent silverskin, and 3 represent monocrystal silicon substrate;
Fig. 2 (a): the cycle is 792nm, highly is the flat scanning Electronic Speculum figure of the nano-cone array of 7.1 μ m;
Fig. 2 (b): the cycle is 792nm, highly is the inclination angle sem photograph of the nano-cone array of 7.1 μ m;
Fig. 2 (c): the cycle is 792nm, highly is the cross section sem photograph of the nano-cone array of 7.1 μ m;
Fig. 3: the transmission electron microscope picture of hollow nanocone;
Fig. 4: the cycle is 792nm, highly is the inclination angle sem photograph of the nano-cone array of 3.4 μ m;
Fig. 5: the cycle is 792nm, highly is the inclination angle sem photograph of the nano-cone array of 2.1 μ m;
Fig. 6 (a): hollow silicon nano-cone array is composed to the specular light in the 2500nm scope at 250nm;
Solid black lines is the specular light spectral curve of monocrystalline silicon piece, the grey solid line is for being 2.1 μ m, cycle to be the specular light spectral curve of the hollow silicon nano-cone array of 792nm highly, and black dotted lines is to be 7.1 μ m, cycle to be the specular light spectral curve of the hollow silicon nano-cone array of 792nm highly;
Fig. 6 (b): hollow silicon nano-cone array is composed to the specular light in 15 mu m ranges at 2.5 μ m;
Solid black lines is the specular light spectral curve of monocrystalline silicon piece, the grey solid line is for being 2.1 μ m, cycle to be the specular light spectral curve of the hollow silicon nano-cone array of 792nm highly, and black dotted lines is to be 7.1 μ m, cycle to be the specular light spectral curve of the hollow silicon nano-cone array of 792nm highly;
Fig. 7: the integrating sphere reflectance spectrum of hollow silicon nano-cone array in 250nm arrives the 1000nm scope;
The grey solid line is for being 2.1 μ m, cycle to be the integrating sphere reflectance spectrum curve of the hollow silicon nano-cone array of 792nm highly, and solid black lines is to be 7.1 μ m, cycle to be the integrating sphere reflectance spectrum curve of the hollow silicon nano-cone array of 792nm highly;
Fig. 8: the optical photograph of monocrystalline silicon piece (left side) and hollow silicon nano-cone array (right side);
Fig. 9 (a): the cycle is that 650nm, end diameter are 547nm, highly are the flat scanning Electronic Speculum figure of the nano-cone array of 4.8 μ m;
Fig. 9 (b): the cycle is that 650nm, end diameter are 547nm, highly are the cross section sem photograph of the nano-cone array of 4.8 μ m;
Figure 10: the cycle is that 650nm, end diameter are 547nm, highly are the cross section sem photograph of the nano-cone array of 2.9 μ m;
Figure 11: the cycle is that 650nm, end diameter are 547nm, highly are the cross section sem photograph of the nano-cone array of 5.7 μ m;
Figure 12: the cycle is that 650nm, end diameter are 547nm, highly are the cross section sem photograph of the nano-cone array of 6.1 μ m;
Figure 13 (a): the cycle is that 650nm, end diameter are 502nm, highly are the flat scanning Electronic Speculum figure of the nano-cone array of 4.5 μ m;
Figure 13 (b): the cycle is that 650nm, end diameter are 502nm, highly are the cross section sem photograph of the nano-cone array of 4.5 μ m;
Figure 14 (a): the cycle is that 650nm, end diameter are 502nm, highly are the flat scanning Electronic Speculum figure of the nano-cone array of 3.5 μ m;
Figure 14 (b): the cycle is that 650nm, end diameter are 502nm, highly are the cross section sem photograph of the nano-cone array of 3.5 μ m;
Figure 15: the cycle is that 650nm, end diameter are 502nm, highly are the cross section sem photograph of the nano-cone array of 5.7 μ m.
The specific embodiment
The present invention is further elaborated below in conjunction with embodiment, rather than will limit the invention with this.
Embodiment 1:
1. the preparation method of polystyrene microsphere:
Under nitrogen protection; with 100 milliliters absolute ethyl alcohols and 40 ml deionized water is decentralized medium; with 10.5 milliliters of styrene; 0.2222 the potassium peroxydisulfate of gram; 0.2445 the dodecyl sodium sulfate of gram; add and be equipped with in the reactor of mechanical agitator and reflux condensing tube, mechanical agitation speed is at 300 rev/mins.Carry out dispersion polymerization in 70 ℃ water-bath, react the emulsion that obtains stablizing milky monodisperse polystyrene microsphere after 10 hours, diameter of micro ball is 792 nanometers.
2. the preparation of polystyrene colloid monolayer crystal:
With the polystyrene microsphere centrifuge washing that makes, be absolute ethyl alcohol and the dispersion of deionized water mixed solution of 1.5:1 again with volume ratio, getting solid content is the emulsion of 0.5% (mass fraction) monodisperse polystyrene microsphere, get the emulsion of 50 microlitres with syringe, be added drop-wise to the diameter that fills deionized water slowly and be in 9 centimetres the glass culture dish, drip 20 microlitre mass percentage concentration again and be 5.0% sodium dodecyl sulfate solution; The monocrystalline silicon piece substrate of handling with step 1 clean and surface hydrophilic picks up the polystyrene individual layer of keeping afloat, and after the air dry, has just obtained the polystyrene colloid crystal of individual layer, and thickness is 792 nanometers.
3. the preparation of hollow silicon nano column array:
With reactive ion etching closelypacked polystyrene colloid crystal is become non-closelypacked colloidal crystal, etching power is RF30W, ICP300W, and chamber pressure is 10mTorr, and oxygen flow is 50SCCM, etch period is 75 seconds, substrate is heated 10 minutes in 120 ℃ of baking ovens again; In substrate, deposit the thick silverskin of 40nm with the vacuum evaporation instrument again; Afterwards substrate is immersed middle the processing 16 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
4. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 180 seconds.The height that obtains nano-cone array is 7.1 μ m, and end diameter is 686nm, and the cycle is 792nm, and draw ratio is 11.Shown in Fig. 2,3; The specular light spectrum is shown in the grey solid line among Fig. 6, the integrating sphere reflectance spectrum is shown in the solid black lines among Fig. 7, the more smooth monocrystalline silicon piece of the reflected value of silicon hollow nano-cone array reduces much as can be seen, it is 0.15% in the 400nm scope that minute surface is reflected in 250nm, in 250nm arrives the 1600nm scope less than 1%; It is interior less than 2% to the 1000nm scope that integrating sphere is reflected in 250nm; Sample as shown in Figure 8, smooth monocrystalline silicon piece can reflecting paper on the picture of letter, silicon hollow nano-cone array then can not.
Embodiment 2:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 1.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, deposits the thick silverskin of 45nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 12 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 120 seconds.The height that obtains nano-cone array is 3.4 μ m, and the cycle is 792nm, and end diameter is 686nm, and draw ratio is 5, as shown in Figure 4.
Embodiment 3:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 1.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, deposits the thick silverskin of 40nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 6 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 90 seconds.The height that obtains nano-cone array is 2.1 μ m, and the cycle is 792nm, and end diameter is 686nm, and draw ratio is 3, as shown in Figure 5; The specular light spectrum is shown in the black dotted lines among Fig. 6, and the integrating sphere reflectance spectrum is shown in the grey solid line among Fig. 7.
Embodiment 4:
1. the preparation method of polystyrene microsphere:
Under nitrogen protection, be decentralized medium with 100 milliliters absolute ethyl alcohols and 40 ml deionized water, with 9 milliliters of styrene; 0.2 the potassium peroxydisulfate of gram; 0.22 the dodecyl sodium sulfate of gram adds and is equipped with in the reactor of mechanical agitator and reflux condensing tube, mechanical agitation speed is at 300 rev/mins.Carry out dispersion polymerization in 70 ℃ water-bath, react the emulsion that obtains stablizing milky monodisperse polystyrene microsphere after 10 hours, diameter of micro ball is 650 nanometers.
2. the preparation of polystyrene colloid monolayer crystal:
With the polystyrene microsphere centrifuge washing that makes, be absolute ethyl alcohol and the dispersion of deionized water mixed solution of 1.5:1 again with volume ratio, obtain the emulsion that solid content is 1.0% (mass fraction), get the emulsion of 100 microlitres with syringe, be added drop-wise to the diameter that fills deionized water slowly and be in 9 centimetres the glass culture dish, Dropwise 50 microlitre concentration is 8.0% sodium dodecyl sulfate solution again; With the clean silicon chip of handling the polystyrene individual layer of keeping afloat is picked up, after the air dry, just obtained the polystyrene colloid crystal of individual layer.
3. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 45 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 38nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 16 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
4. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 150 seconds.The height that obtains nano-cone array is 4.8 μ m, and the cycle is 650nm, and end diameter is 547nm, and draw ratio is 9, as shown in Figure 9.
Embodiment 5:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 45 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 42nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 12 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 120 seconds.The height that obtains nano-cone array is 2.9 μ m, and the cycle is 650nm, and end diameter is 547nm, and draw ratio is 5, as shown in figure 10.
Embodiment 6:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 45 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 45nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 20 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 180 seconds.The height that obtains nano-cone array is 5.7 μ m, and the cycle is 650nm, and end diameter is 547nm, and draw ratio is 10, as shown in figure 11.
Embodiment 7:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 45 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 40nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 30 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 210 seconds.The height that obtains nano-cone array is 6.1 μ m, and the cycle is 650nm, and end diameter is 547nm, and draw ratio is 11, as shown in figure 12.
Embodiment 8:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 60 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 40nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 16 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 150 seconds.The height that obtains nano-cone array is 4.5 μ m, and the cycle is 650nm, and end diameter is 502nm, and draw ratio is 9, as shown in figure 13.
Embodiment 9:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 60 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 40nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 12 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 120 seconds.The height that obtains nano-cone array is 3.5 μ m, and the cycle is 650nm, and end diameter is 502nm, and draw ratio is 7, as shown in figure 14.
Embodiment 10:
1. the preparation method of the preparation method of polystyrene microsphere and polystyrene colloid monolayer crystal sees embodiment 4.
2. the preparation of hollow silicon nano column array:
The preparation method of non-closelypacked colloidal crystal sees embodiment 1, and the time of oxygen reactive ion etching is 60 seconds, sample is heated 10 minutes in 120 degree baking ovens again, deposits the thick silverskin of 40nm with the vacuum evaporation instrument in substrate again; Afterwards sample is immersed middle the processing 20 minutes of mixed solution (hydrofluoric acid concentration is 4.6mol/L, and the concentration of hydrogen peroxide is 0.44mol/L) of hydrofluoric acid and hydrogen peroxide, remove silverskin with chloroazotic acid successively, remove polystyrene microsphere with chloroform; Obtain the silicon nano column array of hollow.
3. constructing of hollow silicon nano-cone array:
The hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, and etching power is RF100W, ICP500W, and chamber pressure is 5mTorr, and the fluoroform flow is 30SCCM, and the sulfur hexafluoride flow is 4SCCM, and etch period is 180 seconds.The height that obtains nano-cone array is 5.7 μ m, and the cycle is 650nm, and end diameter is 502nm, and draw ratio is 12, as shown in figure 15.
Claims (7)
1, the preparation method of silicon hollow nano-cone array comprises the steps:
(1) cleaning of monocrystalline silicon piece and surface hydrophilic are handled;
(2) preparation of polystyrene colloid monolayer crystalline substrate: with the size range of dispersin polymerization preparation is after the polystyrene microsphere eccentric cleaning of 300～1000 nanometers, obtains mass percentage concentration after the dispersion and be 0.5～2.0% emulsion; Be added drop-wise to slowly on the glass culture dish that fills deionized water with the emulsion of syringe again, drip 20～50 microlitre mass percent concentrations again and be 2.0～8.0% sodium dodecyl sulfate solution the above-mentioned concentration of 50～100 microlitres; With the monocrystalline silicon piece substrate polystyrene individual layer of keeping afloat is picked up, after the air dry, just obtained the polystyrene colloid crystalline substrate of individual layer;
(3) constructing of hollow silicon nano column array: with reactive ion etching closelypacked polystyrene colloid crystal is become non-closelypacked colloidal crystal, then substrate was heated 10～15 minutes in 120～150 ℃ of baking ovens; In substrate, deposit the thick silverskin of 35～55nm again, afterwards substrate is immersed in the mixed solution of hydrofluoric acid and hydrogen peroxide and handled 6～30 minutes, remove silverskin with chloroazotic acid successively again, remove polystyrene microsphere, promptly obtain the silicon nano column array of hollow with chloroform;
(4) constructing of hollow silicon nano-cone array: the hollow silicon nano column array that obtains is carried out the reactive ion etching of fluorine, obtain hollow silicon nano-cone array at last, the cycle is adjustable to 800 nanometers from 250 nanometers, and height is adjustable to 7.1 microns from 2.0 microns.
2, the preparation method of silicon hollow nano-cone array as claimed in claim 1, it is characterized in that: the cleaning of the monocrystalline silicon piece described in the step (1) and surface hydrophilic are handled, be silicon chip to be boiled through acetone ultrasonic cleaning 10～15 minutes, absolute ethyl alcohol ultrasonic cleaning 10～15 minutes, oven dry, acidic treatment liquid successively handled 20～30 minutes, again through dry under nitrogen or air atmosphere after the rinsed with deionized water, thereby obtain the monocrystalline silicon piece substrate of cleaning surfaces and hydrophilicity-imparting treatment.
3, the preparation method of silicon hollow nano-cone array as claimed in claim 2 is characterized in that: acidic treatment liquid is the mixed solution of 98% concentrated sulfuric acid and 30% hydrogen peroxide, and the consumption volume ratio of two kinds of solution is 7:3.
4, the preparation method of silicon hollow nano-cone array as claimed in claim 1 is characterized in that: the dispersion described in the step (2) is to be absolute ethyl alcohol and the dispersion of deionized water mixed solution of 1～2.5:1 with volume ratio.
5, the preparation method of silicon hollow nano-cone array as claimed in claim 1, it is characterized in that: the power of the reactive ion etching described in the step (3) is RF20～40W, ICP200～400W, chamber pressure is 5～15mTorr, oxygen flow is 40～60SCCM, and etch period is 30～75 seconds.
6, the preparation method of silicon hollow nano-cone array as claimed in claim 1 is characterized in that: in the mixed solution of hydrofluoric acid described in the step (3) and hydrogen peroxide, hydrofluoric acid concentration is 2.0～5.0mol/L, and the concentration of hydrogen peroxide is 0.20～0.45mol/L.
7, the preparation method of silicon hollow nano-cone array as claimed in claim 1, it is characterized in that: the power of the reactive ion etching of the described fluorine of step (4) is RF50～150W, ICP400～600W, chamber pressure is 5～15mTorr, the fluoroform flow is 20～40SCCM, the sulfur hexafluoride flow is 4～8SCCM, and etch period is 60～210 seconds.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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