CN106145116A - The preparation method of One Dimension Silicon nano wire - Google Patents
The preparation method of One Dimension Silicon nano wire Download PDFInfo
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- CN106145116A CN106145116A CN201510172469.8A CN201510172469A CN106145116A CN 106145116 A CN106145116 A CN 106145116A CN 201510172469 A CN201510172469 A CN 201510172469A CN 106145116 A CN106145116 A CN 106145116A
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Abstract
The open a kind of One Dimension Silicon nanowire preparation method of the present invention, the method comprises the steps: 1) SiO powder is put in heatproof container, then described heatproof container is positioned over the thermal treatment zone of airtight heater；2) clean molybdenum net is positioned in another resistant to elevated temperatures container, then places it in the non-power hot-zone of described airtight heater；3) pressure in described airtight heater is reduced；4) it is filled with protective gas to described airtight heater；5) described heater temperature is risen to 1200-1300 DEG C react；6), after reaction terminates, described heater Temperature fall is made.This method silicon nanowires crystallinity is high, simple to operate, and repeatability is high, and controllability is strong.
Description
Technical field
The present invention relates to the preparation method of One Dimension Silicon nano wire, belong to nanometer semiconductor technology field.
Background technology
Along with being skyrocketed through and the exhaustion day by day of natural resources reserves of demographic and economic, people focus more on the efficient utilization of new forms of energy particularly solar energy.In terms of Solar use, semi-conducting material has advantageous advantage, and they can efficient absorption solar energys be translated into the energy of other forms, such as electric energy, chemical energy etc..Therefore, semi-conducting material can be widely used in the fields such as solaode, photocatalytic water and light degradation.In area of solar cell, how to improve energy conversion efficiency and take into account again cost and be faced with new challenges.In light degradation field, how to improve semi-conducting material the disposal efficiency and reduce its cost become people research emphasis.In follow-up study, people find CdS, CdSe, Cu successively2O and α-Fe2O3Have relative to other material etc. nano material and be preferably catalyzed activity.But, these catalyst face a lot of problem in the application: CdS and CdSe nano material has the strongest toxicity, α-Fe2O3、Cu2O the disposal efficiency is relatively low, and is difficult to improve further.Therefore, Low-cost and eco-friendly semi-conducting material become important topic urgently to be resolved hurrily.
Along with going deep into further of research, research worker finds that nano silicon material has the biggest space excavated, and becomes the important materials solving this problem.Silicon (Si) has typical rutile structure, is the semi-conducting material of a kind of function admirable, rich reserves.Microelectric technique based on silicon-based devices is the pillar of modern information technologies, has been widely used in the numerous areas such as scientific research, quasiconductor and national defense industry.Further, since the demand of device miniaturization, high integration, the size of the silicon materials of use is gradually reduced.nullIn this research process，It is found that the character of One Dimension Silicon nano wire has notable difference with body silicon materials，It not only has nano material distinctive nano effect such as small-size effect、Quantum size effect、Skin effect and Coulomb blockade effect，Also there is the optics not available for body material、The performances such as electricity: (1) band structure changes，Body silicon materials are indirect band-gap semiconductors，Band gap only has 1.12eV，And Schoen D T etc. find that One Dimension Silicon nano wire is direct band-gap semicondictor (Schoen D T,Schoen A P,et.al,High Speed Water Sterilization Using One-Dimensional Nanostructures，Nano Lett,2010,10,3628)；(2) band gap size relies on the diameter of silicon nanowires, as far back as 2003, Lee S T research group proves that the band gap of One Dimension Silicon nano wire and diameter are negative correlativing relation, i.e. reducing along with silicon nanowires diameter, its band gap changes to 3.5eV (Lee S T from 1.1eV, et al.Small-diameter silicon nanowire surfaces [J] .Science, 2003,299:1874-1877)；(3) silicon nanowires has the biggest specific surface area, strong surface activity, and the environmental factors such as illumination and temperature is had the highest sensitivity, utilizes silicon nanowires to make sensor and can detect the change of ammonia, steam, acid-base value and chemical substance.The boron element doped silicon nano wire such as Cui makes field-effect transistor, and can be used for detecting the change of pH, test finds that its electrical conductivity shows as similar linear relation (Cui Y with the pH value of system, Wei Q Q, Park H K, et.al.Nanowire nanosensors for highly sensititive and selective detection of biological and chemical species [J] .Science.2001,293,1289-1293)；(4) excellent photo absorption performance, Chen etc. makees anti-reflection layer with silicon chip surface silicon nanowire array and makes solaode, and its energy conversion efficiency reaches 16.5% (Chen C, Jia R, Yue H H, Li H F, Liu X Y, Wu D Q, Ding W C, Ye T C, Kasai S, Tamotsu H, Chu J H, Wang S L.J.Appl.Phys., 2010,108:094318).(5) sensitive to optical response signal, quick.Zhang etc. pass through experimentation, confirm the phototriode that silicon nanowire array is made, visible and infrared band the illumination of detection has the highest sensitivity, even if the infrared light to special (10-12W) rank of visible ray or micromicrowatt flying watt (10-15W) rank, the obvious signal of telecommunication is had to react (Zhang A, Kim H K, Cheng J, Lo Y H.Nano Lett., 2010,10 (6): 2117-2120).(6) the strongest photocatalytic activity, Shao M W etc. find that One Dimension Silicon nano wire also has outstanding performance (Shao M W in terms of light degradation debirs, Cheng L, et.al, J.Am.Chem.Soc, Excellent Photocatalysis of HF-Treated Silicon Nanowires, 2009,131,17738).Further study show that, form metal-semiconductor contact at surface of silicon nanowires modified metal granule or modify other semiconductor grains and form hetero-junctions and can improve the disposal efficiency of silicon nano composite material to a certain extent.Therefore, find extensive, low cost to prepare high-quality One Dimension Silicon nano wire and become the most necessary.
Common preparation method includes technology (the Volker Schmidt such as chemical gaseous phase deposition, laser ablation, chemical etching, molecular beam epitaxy and supercritical fluid method, Joerg V.Wittemann, et.al, Silicon Nanowires:A Review on Aspects of their Growth and their Electrical Properties, Adv.Mater., 2009,21,2681-2702).In general, the silicon nanowires purity that laser ablation method prepares is higher, but equipment is much more expensive, and production cost is too high, is unfavorable for large-scale production silicon nanowires in reality；Molecular beam epitaxy technique equipment is complicated, and productivity is the lowest, it is difficult to large scale investment produces；Chemistry etch techniques environmental pollution is relatively big, prepares silicon nanowires size relatively thick, and needs monocrystalline silicon piece as substrate, it is impossible to directly applies to other substrates；Supercritical fluid method belongs to solwution method category, relatively costly, and working condition is harsh, and experimentation is complicated.
Accordingly, it is desirable to provide a kind of height simple to operate, repeated and the strong One Dimension Silicon nanowire preparation method of controllability.
Summary of the invention
First technical problem that the invention solves the problems that is to provide a kind of height simple to operate, repeated and the preparation method of the strong One Dimension Silicon nano wire of controllability.
For solving above-mentioned technical problem, the present invention uses following technical proposals:
A kind of One Dimension Silicon nanowire preparation method, it comprises the steps:
1) SiO powder is put in heatproof container, then described heatproof container is positioned over the thermal treatment zone of airtight heater；
2) clean molybdenum net is positioned in another resistant to elevated temperatures container, then places it in the non-power hot-zone of described airtight heater；
3) pressure in described airtight heater is reduced；
4) it is filled with protective gas to described airtight heater；
5) described heater temperature is risen to 1200-1300 DEG C react；
6), after reaction terminates, described heater Temperature fall is made；
The present invention uses silicon monoxide (SiO) pressed powder as silicon source, by chemical vapour deposition technique, prepares high-quality One Dimension Silicon nano wire at the bottom of molybdenum mesh liner.It is characterized in that with highly purified silicon monoxide (SiO) powder be silicon source; high pure metal molybdenum net is substrate; protective gas is carrier gas; silicon monoxide generation dismutation reaction forms silicon and silicon dioxide steam under the high temperature conditions, and on substrate, deposition obtains One Dimension Silicon nano wire (see Fig. 6) then.
Described airtight heater is tube furnace；It is preferably horizontal vacuum tube furnace.
Described heatproof container is the container that can tolerate 1400 DEG C of high temperature, is selected from ceramic boat, porcelain Noah's ark, corundum boat or quartz boat etc., preferably ceramic boat or porcelain Noah's ark.
Thermal source location when the described thermal treatment zone refers to heat described airtight heater；Described non-power hot-zone is the position in airtight heater outside the thermal treatment zone.
The cleannes of molybdenum net have large effect for the formation of nano wire, it is therefore desirable to reach required cleanliness factor by cleaning mode, or other can reach the mode of required cleaning degree.Preferably, after cleaning, molybdenum net needs and dries.It is highly preferred that use dilute hydrochloric acid, dehydrated alcohol and deionized water to clean successively.
Preferably, molybdenum net should place the non-power hot-zone being placed in distance center, thermal treatment zone 10-20cm.
The purity of silicon monoxide powder has impact for the formation of silicon nanowires, should select highly purified silicon monoxide powder, and the purity of the most described silicon monoxide powder is more than 99.9%.
Preferably; with mechanical pump evacuation with pressure in the described heater of reduction; preferably; when pressure is down to 0.1-1Pa; it is filled with protective gas; described protective gas controls in heater during being filled with that pressure is between 10-50Pa, and the speed that is filled with of described protective gas is 50-150 standard cubic centimeters per minute (sccm).Wherein, described protective gas consists of: volume basis is the noble gas of 90%-95% and percent by volume is the hydrogen of 5-10%, and described noble gas is argon, nitrogen, helium or neon.
Preferably, step 5) described heating rate is 15-25 DEG C/min, the time of heating is 2-4 hour.
Preferably, step 6) described in product be prepared One Dimension Silicon nano wire with molybdenum mesh liner at the bottom of the metal-semiconductor contact structure that formed.
Silicon nanowires prepared by the present invention has important application prospect in the fields such as solaode, photocatalysis, photoelectricity.
Beneficial effects of the present invention is as follows:
1, realize grown on larger scale silicon nanowires at the bottom of molybdenum mesh liner first, form the metal-semiconductor contact structure of silicon nanowires and metal molybdenum；
2, silicon nanowires crystallinity is the highest, and the light degradation property preparing sample has the biggest application prospect；
3, simple to operate, raw material, substrate only need to be put in tube furnace by this experiment, are passed through protective gas, set heating schedule, and single step reaction can realize；
4, repeatability is high, and controllability is strong, prepares silicon nanowires success rate in this way on a large scale the highest at the bottom of molybdenum mesh liner；
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1 (a) illustrates low power scanning electron microscope (SEM) image of the One Dimension Silicon nano wire of the molybdenum net Grown of embodiment 1.Fig. 1 (b) illustrates the partial enlargement SEM image of the One Dimension Silicon nano wire of the molybdenum Grown of embodiment 1.
Fig. 2 (a) illustrates low power transmission electron microscope (TEM) image of the One Dimension Silicon nano wire of embodiment 1；Fig. 2 (b) illustrates high resolution transmission electron microscopy (HRTEM) image of the One Dimension Silicon nano wire of embodiment 1；
Fig. 3 illustrates the energy dispersion X ray spectrum figure (EDX) of the One Dimension Silicon nano wire of embodiment 1；
Fig. 4 illustrates the X-ray diffractogram (XRD) of the One Dimension Silicon nano wire of the molybdenum net Grown of embodiment 1.
Fig. 5 illustrates the light degradation aptitude tests result of the sample of embodiment 1.
Fig. 6 illustrates heater schematic diagram
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing are indicated with identical reference.It will be appreciated by those skilled in the art that following specifically described content is illustrative and be not restrictive, should not limit the scope of the invention with this.
Embodiment 1
1. the preparation of silicon nanowires
1) weigh 0.5g SiO powder (purity is 99.9%) and put in ceramic boat, be then placed on the thermal treatment zone of horizontal vacuum tube furnace；
2) by using dilute hydrochloric acid, ethanol and deionized water to dry after cleaning successively at the bottom of molybdenum mesh liner, place in another ceramic boat, will be equipped with the ceramic boat at the bottom of described molybdenum mesh liner and be placed on the non-power hot-zone of horizontal vacuum tube furnace, distance center, thermal treatment zone 10-20cm；
3) open mechanical pump to reduce pressure in described horizontal pipe furnace, pressure is down to 0.1Pa；
4) being passed through in described horizontal vacuum tube furnace by the protective gas (argon and the gaseous mixture of hydrogen) of 100sccm, pressure controls at 50Pa, and wherein argon and hydrogen volume are than for 19:1；
5) the described horizontal pipe furnace thermal treatment zone being risen to 1300 DEG C, programming rate is 20 DEG C/min, 4 hours response time；
6) reaction terminates, and after be naturally cooling to room temperature in described horizontal vacuum tube furnace, takes out sample, at the bottom of molybdenum mesh liner on grown on larger scale silicon nanowires.
As Figure 1-5, wherein Fig. 1 (a) display One Dimension Silicon nano wire has growth in each region of molybdenum net to result；The one-dimensional silicon nanowire distribution that Fig. 1 (b) display prepares is than comparatively dense, and diameter is relatively thin, and length reaches micron order；Fig. 4 result proves that the One Dimension Silicon nano wire that molybdenum grows on the net is silicon, and crystal structure is diamond-type.
2. the degradation capability test of silicon nanowires
By One Dimension Silicon nano wire sample (a size of 2cm of above-mentioned preparation2) put into that to fill the 2mL concentration prepared in advance be 1 × 10-5In the cuvette of the rhodamine liquor of mol/L, in closing space, use 30mW ultra violet lamp cuvette, every 10 minutes, cuvette is taken out and uses the ultraviolet-visible absorption spectroscopy of rhodamine liquor in ultraviolet-uisible spectrophotometer test cuvette.As it is shown in figure 5, there is the rhodamine of about 95% to be degraded in 30min, experimental result explanation calcium One Dimension Silicon nano wire has the strongest light degradation ability.
Embodiment 2: the preparation of silicon nanowires
1) weigh 1g SiO powder (purity is 99.9%) and put in ceramic boat, be then placed on the thermal treatment zone of horizontal vacuum tube furnace；
2) by using dilute hydrochloric acid, dehydrated alcohol and deionized water to dry after cleaning successively at the bottom of molybdenum mesh liner, place in another ceramic boat, will be equipped with the ceramic boat at the bottom of molybdenum mesh liner and be placed on the non-power hot-zone of horizontal vacuum tube furnace, distance center, thermal treatment zone 10-20cm；
3) open mechanical pump to reduce pressure in described horizontal vacuum tube furnace, pressure is down to 0.1P；
4) being passed through in tube furnace by the protective gas (argon and the gaseous mixture of hydrogen) of 80sccm, pressure controls at 30Pa, and wherein said argon and hydrogen volume are than for 19:1；
5) horizontal vacuum tube furnace high-temperature region being risen to 1250 DEG C, programming rate is 20 DEG C/min, 2 hours response time；
6) reaction terminates, and after being naturally cooling to room temperature in described horizontal vacuum tube furnace, takes out sample.
Embodiment 3: the preparation of silicon nanowires
1) weigh 0.8g SiO powder (purity is 99.9%) and put in ceramic boat, be then placed on horizontal vacuum diamond heating district；
2) dilute hydrochloric acid, ethanol and deionized water will be used at the bottom of molybdenum mesh liner to dry after cleaning successively, place in another ceramic boat, will be equipped with the ceramic boat at the bottom of molybdenum mesh liner and be placed on the non-power hot-zone (this is the meaning of the non-thermal treatment zone) of described horizontal pipe furnace, distance center, thermal treatment zone 10-20cm；
3) open mechanical pump to reduce pressure in described horizontal vacuum tube furnace, pressure is down to 1Pa；
4) being passed through in described horizontal vacuum tube furnace by the protective gas (argon and the gaseous mixture of hydrogen) of 150sccm, pressure controls at 30Pa, and wherein said argon and hydrogen volume are than for 19:1；
5) horizontal vacuum diamond heating district being risen to 1275 DEG C, programming rate is 20 DEG C/min, 3 hours response time；
6) reaction terminates, and after being naturally cooling to room temperature in horizontal vacuum tube furnace, takes out sample.
Obviously; the above embodiment of the present invention is only for clearly demonstrating example of the present invention; and it is not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot all of embodiment be given exhaustive, every belong to obvious change that technical scheme extended out or the variation row still in protection scope of the present invention.
Claims (10)
1. One Dimension Silicon nanowire preparation method, it is characterised in that comprise the steps:
1) SiO powder is put in heatproof container, then described heatproof container is positioned over the thermal treatment zone of airtight heater；
2) clean molybdenum net is positioned in another resistant to elevated temperatures container, then places it in the non-power hot-zone of described airtight heater；
3) pressure in described airtight heater is reduced；
4) it is filled with protective gas to described airtight heater；
5) described heater temperature is risen to 1200-1300 DEG C react；
6), after reaction terminates, described heater Temperature fall is made.
Preparation method the most according to claim 1, it is characterised in that: described airtight heater is tube furnace；It is preferably horizontal vacuum tube furnace.
Preparation method the most according to claim 1, it is characterised in that: described heatproof container is the container that can tolerate 1400 DEG C of high temperature, is selected from ceramic boat, porcelain Noah's ark, corundum boat or quartz boat.
Preparation method the most according to claim 1, it is characterised in that: molybdenum net should place the non-power hot-zone being placed in apart from described thermal treatment zone center 10-20cm.
Preparation method the most according to claim 1, it is characterised in that: the purity of described silicon monoxide powder is more than 99.9%.
Preparation method the most according to claim 1, it is characterised in that: in step 3), pressure is down to 0.1-1Pa.
Preparation method the most according to claim 1, it is characterised in that consisting of of described protective gas: percent by volume is the noble gas of 90%-95% and percent by volume is the hydrogen of 5-10%, and described noble gas is argon, nitrogen, helium or neon.
Preparation method the most according to claim 1, it is characterised in that: described protective gas during being filled with in described heater pressure control between 10-50Pa.
Preparation method the most according to claim 1, it is characterised in that: the speed that is filled with of described protective gas is 50-150 standard cubic centimeters per minute.
10.1 preparation methoies according to claim 1, it is characterised in that: step 5) described heating rate is 15-25 DEG C/min, the time of heating is 2-4 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107104357A (en) * | 2017-06-30 | 2017-08-29 | 黄山博蓝特半导体科技有限公司 | A kind of preparation method of nano-sized lasers array |
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| CN102092677A (en) * | 2009-10-20 | 2011-06-15 | 中国科学院理化技术研究所 | Method for oriented growth of one-dimensional inorganic nanowire array on metal substrate |
| CN103290481A (en) * | 2013-06-06 | 2013-09-11 | 四川大学 | Superfine single crystal Si nanowire and preparation method thereof |
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Patent Citations (3)
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| CN101736354A (en) * | 2008-11-06 | 2010-06-16 | 北京有色金属研究总院 | Method for preparing one or more of silicon nano power, silicon nanowires and silicon nanotubes by electrochemical method |
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Non-Patent Citations (1)
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| CN107104357A (en) * | 2017-06-30 | 2017-08-29 | 黄山博蓝特半导体科技有限公司 | A kind of preparation method of nano-sized lasers array |
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