CN100347870C - Electro-luminescent porous silica material and its preparation method - Google Patents
Electro-luminescent porous silica material and its preparation method Download PDFInfo
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- CN100347870C CN100347870C CNB2005100163175A CN200510016317A CN100347870C CN 100347870 C CN100347870 C CN 100347870C CN B2005100163175 A CNB2005100163175 A CN B2005100163175A CN 200510016317 A CN200510016317 A CN 200510016317A CN 100347870 C CN100347870 C CN 100347870C
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Abstract
The present invention discloses electro-luminescent porous silica and a preparation method thereof, which belongs to the technology of electro-luminescent porous silica materials. The electro-luminescent porous silica material is composed of a silica basal layer, a porous silica layer at the top of one side of the silica basal layer and a silica line layer which is arranged on the porous silica layer and has the average diameter of 200 to 500 nanometers and the length of 2 to 10 micrometers. The preparation method comprises the following steps: a cleaned silica chip is put into the water solution of hydrofluoric acid and silver nitrate to be chemically etched, then, the etched silica chip is put into the water solution of hydrofluoric acid and ethanol to be electrically and chemically etched, and the electro-luminescent porous silica material is obtained. The present invention has the advantage of simple preparation process; besides, the obtained electro-luminescent porous silica material has higher luminescent capacity than present electro-luminescent porous silica because of the silica line layer formed at the upper part of the porous silica layer.
Description
Technical field:
The present invention relates to a kind of electro-luminescent porous silica and preparation method thereof, belong to the electro-luminescent porous silica material technology.
Background technology:
Porous silicon is the silicon-based nano luminescent material, since have with existing silicon is integrated easily, development cost is low, emission light evenly, advantage such as polychrome and widely by scientist's research both at home and abroad, and become the main representative of silicon-based nano luminescent material since the nineties in 20th century.
The porous silicon structure of conventional method preparation is common porous column open structure.Preparing this method that has ordinary construction and possess VISIBLE LIGHT EMISSION performance porous silicon mainly contains following several: 1) electrochemistry anodic oxidation.As nineteen ninety L.T.Canham at first is raw material with the silicon chip, adopt electrochemical production to go out the porous silicon that under green laser irradiation, can send ruddiness, referring to L.T.Canham, Appl.Phys.Lett., 57,1046 (1990), and U.S. Patent No. 5348618 and Chinese patent CN 1142875A.2) photochemical corrosion method.Under the effect of light, the monocrystalline silicon that is immersed in the hydrofluoric acid aqueous solution (or hydrofluoric acid ethanolic solution) can react with hydrofluoric acid, and felicity condition can obtain the porous silicon of visible emitting down, referring to Wang Xiaojing, Li Qingshan, Wang Zuochen, luminous journal, 24,203 (2003).3) chemical corrosion method.Silicon chip is immersed in the mixed solution of hydrofluoric acid and oxidant, under the room temperature silicon chip is corroded, can form porous silicon film at monocrystalline silicon surface, referring to Wang Xiaojing, Li Qingshan, Wang Zuochen, luminous journal, 24,203 (2003).But depositing electrode is used for electroluminescent device and but can't obtains higher luminous efficiency on the porous loose structure of this common porous silicon.After the transparency electrode inflow of electric current by top layer, because the semiconductor property of silicon, resistance is bigger, so the less path of electric current inevitable choice resistance, and then electric current will enter silicon substrate by the bottom of porous silicon, flow away by metal back electrode at last.That is, in this case, electric current then participates in the part that luminous porous silicon only is the bottom not by whole porous silicon structure, and the ratio of shared whole porous silicon structure is very little.The electroluminescent device of this structure, its external quantum efficiency only are 0.1%, and maximum also only reaches 0.4%, referring to British patent No.GB2268333B and Chinese patent CN 1185234A.
Summary of the invention:
The object of the present invention is to provide a kind of electro-luminescent porous silica and preparation method thereof, electro-luminescent porous silica luminous efficiency height, the preparation method is simple.
The present invention is realized by following technical proposals, a kind of electro-luminescent porous silica material, it is characterized in that by silicon substrate layer, is porous silicon layer above silicon substrate layer one side, is the 200-500 nanometer, highly constitutes for the silicon line layer of 2-10 micron for average diameter on the porous silicon layer.
The preparation method of above-mentioned electro-luminescent porous silica material is characterized in that comprising following process:
1, be raw material with the p type or the n type monocrystalline silicon piece of any specification, clean up with deionized water, acetone and absolute ethyl alcohol successively, and select one side as etched surface, another side sticks plastic adhesive tape.Place the aqueous solution of 1.0-3.0mol/L hydrofluoric acid and 0.01-0.05mol/L silver nitrate under normal pressure, to be heated to 40-60 ℃ the silicon chip of cleaning, be incubated 30-60 minute and carry out chemical etching.Take out the silicon chip that has been etched, in rare nitric acid of 9-17%, soaked 3-7 days, standby.
2, after the monocrystalline silicon piece that the 1st step was handled soaks in rare nitric acid of 9-17% again in deionized water immersion take out after 5-10 minute and dry.Then the plastic adhesive tape at this silicon chip back side is removed, placed electrolysis tank with the chemical etching face as anode, and add hydrofluoric acid, ethanol and deionized water are 1 according to volume ratio: the electrolyte that 1-10: 1-10 mixes carries out electrochemical etching.Current density during electrochemical etching is controlled at 20-80mA/cm
2, etch period is 20-60 minute.After etching finished, the taking-up silicon chip soaked in absolute ethyl alcohol and dries the electro-luminescent porous silica that promptly obtains to have the silicon line structure after 5-10 minute.
The invention has the advantages that: the porous silica material of preparing forms silicon line layer on porous silicon layer top, when being used for electroluminescence, after electric current flows into from the transparency electrode of top layer, because the existence of silicon line, electric current will all be gone into porous silicon by the silicon linear flow, it is luminous that porous silicon can fully be participated in, thereby have existing electro-luminescent porous silica luminous power more efficiently.
Description of drawings:
Fig. 1: the existing electro-luminescent porous silica material structural representation that constitutes by silicon base layer and porous silicon layer.
Fig. 2: the electro-luminescent porous silica material structural representation of the present invention's preparation.1 is silicon substrate layer among the figure, and 2 is porous silicon layer, and 3 is silicon line layer.
Embodiment:
Embodiment 1:
Adopting p type, boron doping, resistivity is that 10-12 Ω cm, the indices of crystallographic plane are (100), thick, the 1 * 1cm of 2mm
2Monocrystalline silicon piece make raw material.Clean with deionized water, acetone, absolute ethyl alcohol successively, after the oven dry one side is sticked adhesive tape.Preparation etching liquid 3.0mol/L hydrofluoric acid and 0.01mol/L silver nitrate 20ml, under normal pressure, be heated to 50 ℃ after, insert above-mentioned silicon chip, be incubated 60 minutes.Soaked in 10% rare nitric acid 4 days subsequently, take out and adhesive tape is removed after drying, place the anode of electrolysis tank with the one side that is etched, negative electrode is a graphite electrode.Selecting hydrofluoric acid 6ml, ethanol 9ml, deionized water 12ml (volume ratio) for use is etching liquid, with current density 80mA/cm
2Etching obtains to have the electro-luminescent porous silica of silicon line structure after 20 minutes.Silicon line average diameter 235nm, average height 8.5 μ m.
Embodiment 2:
Adopting p type, boron doping, resistivity is that 10-12 Ω cm, the indices of crystallographic plane are (100), thick, the 1 * 1cm of 2mm
2Monocrystalline silicon piece make raw material.Clean with deionized water, acetone, absolute ethyl alcohol successively, after the oven dry one side is sticked adhesive tape.Preparation etching liquid 3.0mol/L hydrofluoric acid and 0.01mol/L silver nitrate 20ml, under normal pressure, be heated to 60 ℃ after, insert above-mentioned silicon chip, be incubated 60 minutes.Soaked in 10% rare nitric acid 4 days subsequently, take out and adhesive tape is removed after drying, place the anode of electrolysis tank with the one side that is etched, negative electrode is a graphite electrode.Selecting hydrofluoric acid 1ml, ethanol 10ml, deionized water 10ml (volume ratio) for use is etching liquid, successively with current density 30mA/cm
2Etching 30 minutes and 20mA/cm
2Etching obtains to have the electro-luminescent porous silica of silicon line structure after 30 minutes.
Embodiment 3:
Adopting p type, boron doping, resistivity is that 10-12 Ω cm, the indices of crystallographic plane are (110), thick, the 1 * 1cm of 2mm
2Monocrystalline silicon piece make raw material.Clean with deionized water, acetone, absolute ethyl alcohol successively, after the oven dry one side is sticked adhesive tape.Preparation etching liquid 1.5mol/L hydrofluoric acid and 0.01mol/L silver nitrate 20ml, under normal pressure, be heated to 40 ℃ after, insert above-mentioned silicon chip, be incubated 60 minutes.Soaked in 10% rare nitric acid 4 days subsequently, take out and adhesive tape is removed after drying, place the anode of electrolysis tank with the one side that is etched, negative electrode is a graphite electrode.Selecting hydrofluoric acid 6ml, ethanol 9ml, deionized water 12ml (volume ratio) for use is etching liquid, successively with current density 30mA/cm
2Etching 30 minutes and 20mA/cm
2Etching obtains to have the electro-luminescent porous silica of silicon line structure after 30 minutes.
Embodiment 4:
Adopting p type, boron doping, resistivity is that 10-12 Ω cm, the indices of crystallographic plane are (110), thick, the 1 * 1cm of 2mm
2Monocrystalline silicon piece make raw material.Clean with deionized water, acetone, absolute ethyl alcohol successively, after the oven dry one side is sticked adhesive tape.Preparation etching liquid 1.0mol/L hydrofluoric acid and 0.05mol/L silver nitrate 20ml, under normal pressure, be heated to 50 ℃ after, insert above-mentioned silicon chip, be incubated 30 minutes.Soaked in 10% rare nitric acid 4 days subsequently, take out and adhesive tape is removed after drying, place the anode of electrolysis tank with the one side that is etched, negative electrode is a graphite electrode.Selecting hydrofluoric acid 6ml, ethanol 9ml, deionized water 12ml (volume ratio) for use is etching liquid, successively with current density 30mA/cm
2Etching 30 minutes and 20mA/cm
2Etching obtains to have the electro-luminescent porous silica of silicon line structure after 30 minutes.
Claims (1)
1. the preparation method of an electro-luminescent porous silica material, described electro-luminescent porous silica material, comprise silicon substrate layer, above silicon substrate layer one side, be porous silicon layer, for average diameter is that 200-500 nanometer, length are the silicon line layer of 2-10 micron, it is characterized in that comprising following process on the porous silicon layer:
1) p type or the n type monocrystalline silicon piece with any specification is raw material, clean up with deionized water, acetone and absolute ethyl alcohol successively, and select one side as etched surface, another side sticks plastic adhesive tape, place the aqueous solution of 1.0-3.0mol/L hydrofluoric acid and 0.01-0.05mol/L silver nitrate under normal pressure, to be heated to 40-60 ℃ the silicon chip of cleaning, be incubated 30-60 minute and carry out chemical etching, take out the silicon chip that has been etched then, in rare nitric acid of 9-17%, soaked 3-7 days, standby;
2) with the 1st) monocrystalline silicon piece handled of step in the rare nitric acid of 9-17%, soaks after again in deionized water immersion take out after 5-10 minute and dry, then the plastic adhesive tape at this silicon chip back side is removed, place electrolysis tank with the chemical etching face as anode, and adding hydrofluoric acid, the second alcohol and water is 1 according to volume ratio: the electrolyte that 1-10: 1-10 mixes carries out electrochemical etching, and the current density during electrochemical etching is controlled at 20-80mA/cm
2, etch period is 20-60 minute, after etching finished, the taking-up silicon chip soaked in absolute ethyl alcohol and dries the electro-luminescent porous silica that promptly obtains to have the silicon line structure after 5-10 minute.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2008045301A1 (en) | 2006-10-05 | 2008-04-17 | Hitachi Chemical Co., Ltd. | Well-aligned, high aspect-ratio, high-density silicon nanowires and methods of making the same |
| CN101973517A (en) * | 2010-10-21 | 2011-02-16 | 东华大学 | Method for preparing low doped porous silicon nanowire array |
| CN102330142B (en) * | 2011-09-05 | 2013-10-30 | 华北电力大学 | Preparation method of nano porous antireflection structure on silicon surface |
| CN103343382A (en) * | 2013-05-28 | 2013-10-09 | 浙江大学 | Down-conversion luminescent porous silicon material, preparation and application thereof |
| CN103865534B (en) * | 2014-03-27 | 2015-09-02 | 浙江理工大学 | A kind of preparation method of nitride fluorescent thin-film material |
| CN108022967A (en) * | 2017-12-01 | 2018-05-11 | 西安交通大学 | A kind of porous silicon nanowire composite structures and preparation method thereof |
| CN108611682A (en) * | 2018-05-07 | 2018-10-02 | 重庆大学 | The preparation method of high-performance n-type porous silicon |
| CN110157409B (en) * | 2019-05-27 | 2022-02-22 | 武汉科技大学 | Porous silicon/carbon quantum dot micro-nano composite material and preparation method thereof |
| CN112573478A (en) * | 2020-12-15 | 2021-03-30 | 苏州大学 | Silicon nanocone array and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019084A1 (en) * | 1991-04-17 | 1992-10-29 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Electroluminescent silicon device |
| US5331180A (en) * | 1992-04-30 | 1994-07-19 | Fujitsu Limited | Porous semiconductor light emitting device |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019084A1 (en) * | 1991-04-17 | 1992-10-29 | The Secretary Of State For Defence In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Electroluminescent silicon device |
| US5331180A (en) * | 1992-04-30 | 1994-07-19 | Fujitsu Limited | Porous semiconductor light emitting device |
Non-Patent Citations (1)
| Title |
|---|
| 多孔硅的不同制备方法及其光致发光 王晓静，李清山，王佐臣.发光学报，第24卷第2期 2003 * |
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