CN102815701A - Preparation method of one-dimensional silicon nanowires with different linear densities - Google Patents
Preparation method of one-dimensional silicon nanowires with different linear densities Download PDFInfo
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- CN102815701A CN102815701A CN2012103253811A CN201210325381A CN102815701A CN 102815701 A CN102815701 A CN 102815701A CN 2012103253811 A CN2012103253811 A CN 2012103253811A CN 201210325381 A CN201210325381 A CN 201210325381A CN 102815701 A CN102815701 A CN 102815701A
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Abstract
The invention discloses a preparation method of one-dimensional silicon nanowires with different linear densities. The method includes following steps of, a, preprocessing a silicon chip; b, preparing a one-dimensional silicon nanowire array by means of a metal catalysis etching method; and c, performing postprocessing, wherein the metal catalysis etching method includes two steps of, step one, depositing silver nanoparticles: impregnating the preprocessed silicon chip in an HF-AgNO3 mixed aqueous solution for 20-40 seconds, the concentration of HF is 0.1-0.2 mol/L, and the concentration of AgNO3 is 0.008-0.012 mol/L; and step two, performing metal assisted etching: immersing the silicon chip obtained from the step one into an HF-H2O2 mixed etching solution, and performing etching for 20-40 minutes under a room temperature. According to the preparation method of the one-dimensional silicon nanowires with the different linear densities, the photoelectric properties of the prepared one-dimensional silicon nanowire array are obviously improved in ultraviolet diffuse reflection, photocurrent characteristics and photocatalysis reaction, technological parameters can be adjusted to control shapes and densities of the silicon nanowires, and the preparation method is simple, low in cost and pollution-free.
Description
Technical field
The invention belongs to field of photocatalytic material, relate in particular to the preparation method of one dimension silicon nanowires (SiNWs) array of different linear densities.
Background technology
Environmental pollution and energy shortage are the significant challenge that current mankind faces.Photocatalytic process can convert inexhaustible low density solar energy into highdensity chemical energy and electric energy; Physicochemical change degraded mineralized water and airborne most pollutent that can also directly utilize sunshine and photocatalyst material effect to be taken place simultaneously, thereby photochemical catalysis demonstrates great potential at aspects such as environmental purification and new energy developments.The photocatalyst material catalytic activity is high with stability, low price, and environmental friendliness is fully developed talents in environmental pollution control field.In recent years, about semi-conductor TiO
2Research show that it has great potential in photocatalysis field.But it is because the energy gap of its broad, thereby very limited for the utilization ratio of luminous energy.
Compare TiO
2Wait other semiconductor material, silicon (Eg=1.12 eV) can be a large amount of utilizes the light photon energy in the sunshine.Its Photocatalytic Performance Study starting just begins to be in the news from 2009 than later.Research shows that it is compound that the narrower energy gap of silicon has caused its light induced electron-hole very easily to take place, and photoelectric transformation efficiency reduces, and nanometer is the effective way that addresses this problem.Yet though silicon nano material has bigger specific surface area, its surface is contaminated easily, and when it immerses in the aqueous solution, adsorbs easily-OH and by hydroxylation.Even when pure silicon nano material long-term exposure is in moistening air maybe with O
2Form SiO etc. adsorption and diffusion
xNano wire influences the absorption of silicon nano material to light.Therefore at uv drs, photoelectric properties are relatively poor in photocurrent characteristics and the light-catalyzed reaction process.
Summary of the invention
Goal of the invention: to the problem and shortage of above-mentioned existing existence; The preparation method who the purpose of this invention is to provide a kind of one-dimensional nano line of different linear densities; The one-dimensional nano line array that this method obtains has good light catalysis and absorptive character; And can be through the pattern and the density of adjusting process parameter control silicon nanowires, the preparation method is simple, with low cost pollution-free.
Technical scheme: for realizing the foregoing invention purpose; The present invention adopts following technical scheme: a kind of preparation method of one dimension silicon nanowires of different linear densities; May further comprise the steps: the pre-treatment of a, silicon chip: silicon chip is after cleaning; Immerse the zone of oxidation of removing the surface in the hydrofluoric acid solution, and dry up with hydrogen; B, metal catalytic etching method prepare the one dimension silicon nanowire array, two steps below dividing: the first step, depositing silver nano particle: will be through pretreated silicon chip in HF-AgNO
3Mixed aqueous solution in flood 20～40s, wherein the concentration of HF is 0.1～0.2mol/L, AgNO
3Concentration be 0.008～0.012mol/L; Second one, metal auxiliary etch: the first step is obtained silicon chip immerse HF-H
2O
2The mixing etching liquid in, and etching 20～40min at room temperature; C, aftertreatment: the silicon chip that etching is intact places HNO
3In the solution, remove sedimentary Ag particle, use washed with de-ionized water then, dry down at 60 ℃ at last.
In present method, said HF-H
2O
2The mixing etching liquid in the volume percent of each component following: 20% HF, 10～30% H
2O
2, and the water of surplus.
Beneficial effect: compared with prior art, key point of the present invention is the adjustability of prepared one dimension SiNWs array parameter, and than the body silicon materials, it is at uv drs, and photoelectric properties are significantly improved in photocurrent characteristics and the light-catalyzed reaction process:
(1) one dimension SiNWs array preparation method materials of the present invention are simple, and preparation technology is easy and simple to handle, need not complicated synthesis device, and cost is low;
(2) through regulating H in the etching liquid
2O
2Concentration can obtain the one dimension SiNWs array of different linear densities, its shape characteristic influences its photoelectric properties;
(3) because silicon has narrower energy gap, so this SiNWs can both be excited with under the visible light at UV-light.The photocatalysis performance that excites the light induced electron that produced and hole can effectively improve this structure;
(4) this SiNWs has very strong light absorpting ability: the body silicon materials can reflect 35% incident light, and prepared SiNWs is owing to falling into photoeffect, to reflection of light almost nil (like Fig. 3).Explain that nano thread structure more helps its collection and utilization to light;
(5) the prepared SiNWs of photoelectric current test shows is for the body silicon materials, and photoelectric current obviously improves (like Fig. 4);
(6) this SiNWs photocatalysis performance is improved: nanostructure is owing to have physico-chemical properties such as small-size effect, surface effects, quantum size effect, macro quanta tunnel effect and dielectric confinement effect, thereby can improve the photoelectric properties of body silicon materials.The photochemical catalysis curve shows that nanometer has overcome the defective on the body silicon material structure, makes its photodegradation ability obtain bigger improvement.
Description of drawings
Fig. 1 is 10% H
2O
2The SEM photo of the SiNWs of etching preparation, wherein (a) and the low enlargement ratio that (b) is respectively vertical view (SiNWs is surperficial) and the SEM image of high enlargement ratio; (c), (d) is respectively the low enlargement ratio of sectional view (SiNWs section) and the SEM image of high enlargement ratio;
Fig. 2 is 20% and 30% H
2O
2The SEM photo of the SiNWs of etching preparation, wherein (a) and (b) be respectively 20% H
2O
2The SiNWs of etching preparation is at the SEM image of low enlargement ratio and high enlargement ratio; (c), (d) is respectively 30% H
2O
2The SiNWs of etching preparation low enlargement ratio and high enlargement ratio the SEM image;
Fig. 3 is the ability spectrogram of the prepared SiNWs of the present invention;
Fig. 4 is body silicon materials and 10% H
2O
2The uv drs collection of illustrative plates of the SiNWs of etching preparation;
Fig. 5 is body silicon materials and 10% H
2O
2The photoelectric current test curve of the SiNWs of etching preparation;
Fig. 6 is different concns H
2O
2The SiNWs photochemical catalysis result of etching preparation.Wherein, (a) and (b) with (c) be respectively 10%, 20% and 30% H
2O
2The SiNWs photochemical catalysis result of etching preparation (d) is above-mentioned three kinds of H
2O
2The SiNWs photochemical catalysis of concentration etching preparation relatively.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment; Further illustrate the present invention; Should understand these embodiment only be used to the present invention is described and be not used in the restriction scope of the present invention; After having read the present invention, those skilled in the art all fall within the application's accompanying claims institute restricted portion to the modification of the various equivalent form of values of the present invention.
Embodiment 1:
1), the pre-treatment of silicon chip: after the silicon chip cutting, it is ultrasonic to place acetone soln to clean earlier, uses washed with de-ionized water, immerses the HF/H that volume ratio is 1:10 then
2After 15 min remove thin oxide layer in the solution of O, dry up with hydrogen;
2), adopt the metal catalytic etch to prepare one dimension SiNWs array, be divided into following two steps:
The first step, depositing silver nano particle: will be through pretreated silicon chip in 0.14 mol/L HF and 0.01 mol/L AgNO
3Flood 30s in the mixing solutions;
Second step, metal auxiliary etch: the silicon base of depositing silver nano particle is immersed HF-H
2O
2-H
2In the mixing etching liquid of O volume ratio 20:10:70, etching 30 min promptly obtain 10% SiNWs under the room temperature;
3), one dimension SiNWs array aftertreatment: the silicon chip after the etching completion is placed HNO
3In the solution, remove sedimentary Ag particle, use washed with de-ionized water then, under 60 ℃, dry in vacuum drying oven at last.Can obtain nanowire length and be about 16 μ m, diameter is about the one dimension SiNWs array of 150 nm;
4), the pattern of prepared SiNWs characterizes (SEM) and photoelectric properties tests (DSR, photoelectric current, photochemical catalysis etc.).
Embodiment 2:
1), the pre-treatment of silicon chip (with embodiment 1);
2), adopt the metal catalytic etch to prepare one dimension SiNWs array, be divided into following two steps:
The first step, depositing silver nano particle: will be through pretreated silicon chip in 0.14 mol/L HF and 0.01 mol/L AgNO
3Flood 30s in the mixing solutions;
Second step, metal auxiliary etch: the silicon base of depositing silver nano particle is immersed HF-H
2O
2-H
2In the mixing etching liquid of O volume ratio 20:20:60, etching 30 min promptly obtain 20% SiNWs under the room temperature;
3), one dimension SiNWs array aftertreatment (with embodiment 1);
4), sample characterization and photoelectric properties tests (with embodiment 1).
Embodiment 3:
1), the pre-treatment of silicon chip (with embodiment 1);
2), adopt the metal catalytic etch to prepare one dimension SiNWs array, be divided into following two steps:
The first step, depositing silver nano particle: will be through pretreated silicon chip in 0.14 mol/L HF and 0.01 mol/L AgNO
3Flood 30s in the mixing solutions;
Second step, metal auxiliary etch: the silicon substrate of depositing silver nano particle is immersed HF-H
2O
2-H
2In the mixing etching liquid of O volume ratio 20:30:50, etching 30 min promptly obtain 30% SiNWs under the room temperature;
3), one dimension SiNWs array aftertreatment (with embodiment 1);
4), sample characterization and photoelectric properties tests (with embodiment 1).
Can know 10% H through SEM figure
2O
2The one dimension SiNWs length of etching preparation is about 16 μ m, and diameter is about 150 nm; The nano wire gap is bigger, and density is bigger.20% H
2O
2The SiNWs length of etching preparation is consistent with 10% SiNWs with diameter, and the surface is vesicular; The nano wire gap is bigger, and density is less.30% H
2O
2Etching obtains the porous silicon structure.
Fig. 1 is 10% H
2O
2The SEM photo of the SiNWs of etching preparation.The figure (a) and (b) are respectively the low enlargement ratio of silicon nanowires vertical view and the SEM image of high enlargement ratio.(c), (d) is respectively the low enlargement ratio of silicon nanowires sectional view and the SEM image of high enlargement ratio.(a) white portion is the top of prepared nano-wire array in; Agglomeration appears in the silicon nanowires top; Black region is the gap between the nano wire, and (c) sectional view then demonstrates the form of " nano wire forest ", does not obviously observe the silicon nanowires agglomeration shown in the front.The length that can be observed prepared nano wire by (c), (d) concentrates on about 16 μ m, and diameter is about 150 nm.By can spectrogram among the figure (e) seeing, only contain Si element (due to metal spraying was introduced when wherein the peak of Au was sweep test) among the prepared SiNWs, other impurity elements not, the surface prepared nano wire be purified silicon nanowires (SiNWs).These characterize all explanations, make the body silicon materials structurally realize nanometer through etching reaction, have given the body silicon materials reasonable nano-wire array, for reliable architecture basics has been established in the improvement on its performance.
Fig. 2 is 20% and 30% H
2O
2The SEM photo of the SiNWs of etching preparation.The figure (a) and (b) are respectively 20% H
2O
2The SiNWs of etching preparation is at the SEM image of low enlargement ratio and high enlargement ratio; (c), (d) is respectively 30% H
2O
2The SiNWs of etching preparation low enlargement ratio and high enlargement ratio the SEM image.Comparison diagram 1 can find out that with Fig. 2 (a) and (b) 20% SiNWs diameter is constant basically, and nano wire gap and hole are all bigger, and relatively the dispersive structure more helps the incident and the absorption of light.30% H
2O
2Etching obtains the porous silicon structure.This possibly be because H
2O
2Concentration excessive, in the etching reaction vertically etching strengthen, influence the directivity of vertical etching.
Fig. 3 is body silicon materials and H
2O
2Content is the uv drs collection of illustrative plates of the SiNWs of etching preparation in 10% the etching liquid.10% H
2O
2The SiNWs of etching preparation is almost nil to reflection of incident light in whole light area.This explanation nanometer process makes the optical property of proper silicon materials obtain very big improvement, and nanostructure makes its receptivity to light all be greatly improved.
Fig. 4 is body silicon materials and H
2O
2Content is the photoelectric current test curve of the SiNWs of etching preparation in 10% the etching liquid.By finding out among the figure, under illumination condition, the silicon of nanometer is than the body silicon materials, and photoelectric current improves a lot (10% SiNWs:0.35 mA; Si:0.09 mA).Explanation is for the body silicon materials, and making up nano thread structure is the effective way that improves its photoelectric properties.
Fig. 5 is different concns H
2O
2Etching prepares SiNWs photochemical catalysis result.(a) (b) (c) is respectively 10%, 20% and 30% SiNWs photochemical catalysis result, (d) is three kinds of H
2O
2The concentration etching prepares the SiNWs photochemical catalysis relatively.Can find out that the photo-catalysis capability of 20% SiNWs that pattern is best is the strongest; 10% SiNWs that nano wire is the reunion shape takes second place, 30% H
2O
2The photochemical catalysis effect of the porous silicon structure of etching preparation is the poorest.Above-mentioned shape characteristic shows, suitable raising H
2O
2Concentration (20%) helps to reduce the density of prepared nano wire, thereby helps the incident and the absorption of light, and improves the contact area of nano wire and pollutent, thereby improves its photocatalysis efficiency.But, work as H
2O
2(reach 30%) when concentration is excessive, be unfavorable for the formation of nano thread structure on the contrary.
Claims (2)
1. the preparation method of the one dimension silicon nanowires of different linear densities is characterized in that may further comprise the steps:
The pre-treatment of a, silicon chip: silicon chip immerses the zone of oxidation of removing the surface in the hydrofluoric acid solution after cleaning, and dries up with hydrogen;
B, metal catalytic etching method prepare the one dimension silicon nanowire array, two steps below dividing:
The first step, depositing silver nano particle: will be through pretreated silicon chip in HF-AgNO
3Mixed aqueous solution in flood 20～40s, wherein the concentration of HF is 0.1～0.2mol/L, AgNO
3Concentration be 0.008～0.012mol/L;
Second one, metal auxiliary etch: the first step is obtained silicon chip immerse HF-H
2O
2The mixing etching liquid in, and etching 20～40min at room temperature;
C, aftertreatment: the silicon chip that etching is intact places HNO
3In the solution, remove sedimentary Ag particle, use washed with de-ionized water then, dry down at 60 ℃ at last.
2. according to the preparation method of the one dimension silicon nanowires of the said different linear densities of claim 1, it is characterized in that: said HF-H
2O
2The mixing etching liquid in the volume percent of each component following: 20% HF, 10～30% H
2O
2, and the water of surplus.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342337A (en) * | 2013-07-11 | 2013-10-09 | 昆明理工大学 | Method for preparing mesoporous silicon nanowire by metal nanoparticle auxiliary etching method |
| CN103464146A (en) * | 2013-09-29 | 2013-12-25 | 重庆大学 | Pt/silicon nanometer array structure composite material and preparation method thereof |
| CN103746038A (en) * | 2014-01-09 | 2014-04-23 | 上海交通大学 | Preparation method of porous silicon template |
| CN105428432A (en) * | 2015-11-06 | 2016-03-23 | 上海师范大学 | Preparation method for porous light-trapping structure on surface of silicon solar cell |
| CN105854876A (en) * | 2016-04-22 | 2016-08-17 | 大连理工大学 | Preparation method for silicon photocatalyst with 3D multilevel structure |
| CN114164456A (en) * | 2021-12-08 | 2022-03-11 | 昆明理工大学 | Method for preparing composite silicon nano-structure catalyst by using industrial waste silicon powder and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693191A (en) * | 2005-05-20 | 2005-11-09 | 清华大学 | Process for preparing monocrystalline silicon nano line array with single axial arranging |
| CN102560493A (en) * | 2012-01-18 | 2012-07-11 | 电子科技大学 | Method for preparing silicon nanowire array |
-
2012
- 2012-09-05 CN CN2012103253811A patent/CN102815701A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1693191A (en) * | 2005-05-20 | 2005-11-09 | 清华大学 | Process for preparing monocrystalline silicon nano line array with single axial arranging |
| CN102560493A (en) * | 2012-01-18 | 2012-07-11 | 电子科技大学 | Method for preparing silicon nanowire array |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103342337A (en) * | 2013-07-11 | 2013-10-09 | 昆明理工大学 | Method for preparing mesoporous silicon nanowire by metal nanoparticle auxiliary etching method |
| CN103342337B (en) * | 2013-07-11 | 2016-01-20 | 昆明理工大学 | Metal nanoparticle auxiliary etch legal system is for the method for nanometer line |
| CN103464146A (en) * | 2013-09-29 | 2013-12-25 | 重庆大学 | Pt/silicon nanometer array structure composite material and preparation method thereof |
| CN103464146B (en) * | 2013-09-29 | 2015-06-17 | 重庆大学 | Pt/silicon nanometer array structure composite material and preparation method thereof |
| CN103746038A (en) * | 2014-01-09 | 2014-04-23 | 上海交通大学 | Preparation method of porous silicon template |
| CN105428432A (en) * | 2015-11-06 | 2016-03-23 | 上海师范大学 | Preparation method for porous light-trapping structure on surface of silicon solar cell |
| CN105854876A (en) * | 2016-04-22 | 2016-08-17 | 大连理工大学 | Preparation method for silicon photocatalyst with 3D multilevel structure |
| CN114164456A (en) * | 2021-12-08 | 2022-03-11 | 昆明理工大学 | Method for preparing composite silicon nano-structure catalyst by using industrial waste silicon powder and application |
| CN114164456B (en) * | 2021-12-08 | 2023-08-08 | 昆明理工大学 | Method for preparing composite silicon nanostructure catalyst by utilizing industrial waste silicon powder and application |
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