CN100375235C - Growth controlling method for preparation of silicon dioxide or silicon nanowire in large area - Google Patents
Growth controlling method for preparation of silicon dioxide or silicon nanowire in large area Download PDFInfo
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- CN100375235C CN100375235C CNB2005100045732A CN200510004573A CN100375235C CN 100375235 C CN100375235 C CN 100375235C CN B2005100045732 A CNB2005100045732 A CN B2005100045732A CN 200510004573 A CN200510004573 A CN 200510004573A CN 100375235 C CN100375235 C CN 100375235C
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Abstract
The present invention relates to a growth controlling method for preparation of silicon dioxide or silicon nanowires in large area. The present invention comprises the following procedures: step 1, the underlay of a single crystal silicon wafer is deposited with an amorphous film with the method of physical vapor deposition, magnetron sputtering or chemical vapour deposition; step 2, then flowing mixed gas of N2 and Ar or N2, H2 and Ar and H2 are charged into a reaction cavity of a sealing quartz tube as protective gas; step 3, the single crystal silicon wafer with the amorphous film is directly annealed to be deposited, and the silicon substrate is grown with the silicon dioxide/the silicon nanowires in large area; step 4, the deposited amorphous silicon oxide film is provided with a slot which is exposed out of the substrate of the single crystal silicon with photo-etch process and wet etching, and the width of the slot is the width a plurality of microns; step 5, then the flowing protective gas is charged into a reaction chamber of the sealing quartz tube, and the substrate of the single crystal silicon is orderly grown with the silicon dioxide/the silicon nanowires in large area in the direction which is perpendicular to the slot.
Description
Technical field
The present invention relates to a kind of preparation method of low-dimension nano material, the method for particularly a kind of large-area preparation silicon dioxide or silicon nanowires and control growing thereof belongs to nano material preparation and applied technical field.
Background technology
Silicon materials at traditional microelectronic industry in occupation of critical role, silicon nanowires is as the one-dimensional nano structure of silicon, because of its band structure, optics and electrons transport property, very big application prospect is arranged aspect (light) electronic device, interconnection line, the senser element and become a big research focus receiving.The amorphous carbon/silicon dioxide nano wire is observed strong blue light because of it in room temperature, also can be used widely in the integrated electro field of nanometer devices, receives much concern equally.Nanometer silica line can pass through silica white nano-wire, perhaps adopts low vacuum degree to obtain in preparation silicon nanowires process, so the preparation method of silicon nanowires and nanometer silica line is similar.The conventional method for preparing the silicon/silicon dioxide nano wire is divided into top-down template, as the Lithographic template method [referring to the special application number 03141848.1 of China, publication number CN 1474434A] and self-assembly method from bottom to top, as metal catalytic VLS (Vapor-liquid-solid) mechanism [referring to Chinese patent application number 02104179.2, publication number CN 1382626A].Oxide assisting growth OAG (Oxide-assisted growth) the self assembly mechanism that proposes is to adopt high temperature evaporation or pulse to swash ablation SiO recently
2With Si mixed-powder or SiO high-purity powder, collect a kind of straightforward procedure of silicon/silicon dioxide nano wire [referring to R.Q.Zhang from chamber wall or substrate, Y.Lifshitz and S.T.Lee, Adv.Mater., 15,635 (2003)], advantage is to avoid adopting metal or metallic compound as catalyst, but incompatible with silicon planar technique technology.
The controllable growth of nano wire is the necessary condition that realizes nanometer (light) electric device.The orderly preparation and the controllable growth of nano wire mainly contain Lithographic template method [referring to the special application number 03141848.1 of China, publication number CN 1474434A] and alumina formwork method [referring to the special application number 01113646.4 of China, publication number CN 1323051A] at present.The former is strict to process equipment, and generation yields poorly, the cost height; Latter's preparation process complexity, operation are difficult for grasping.
Summary of the invention
The control growing method that the purpose of this invention is to provide large-area preparation silicon dioxide or silicon nanowires has that technology and equipment are simple, heat treatment temperature is low, growth in situ, and controllable doped P type or N type are with advantages such as silicon integrated technique compatibilities.
The control growing method of a kind of large-area preparation silicon dioxide of the present invention or silicon nanowires is characterized in that, comprises the steps:
Step 1: on the monocrystalline silicon piece substrate, deposit one deck noncrystalline membrane with physical vaporous deposition, magnetron sputtering method or chemical vapour deposition technique;
Step 2: use photoetching process and wet etching on the amorphous state silicon oxide film of deposition, leave several microns wide groove, expose monocrystalline substrate;
Step 3: in airtight quartz ampoule reaction chamber, charge into mobile N then
2, Ar or N
2And H
2, Ar and H
2Mist is as protective gas;
Step 4: annealing back vertical trench direction ordering growth on monocrystalline substrate goes out large-area silica/silicon nano wire.
Wherein the thickness of noncrystalline membrane is 10～600nm, and noncrystalline membrane is SiO
xThe material of 0＜X≤2 wherein.
Wherein the flow of protective gas is 50～500sccm.
Annealing temperature wherein is under 1000～1300 ℃ of temperature, and the time is 1～5hrs.
The large-area silica/silicon nano wire that wherein grows on monocrystalline substrate is of a size of 10mm * 10mm, and the diameter of its nano wire is at 20～100nm, and length surpasses 100 μ m.
Wherein during grow silicon nanowires, the reative cell vacuum remains on 200～500Torr.
Beneficial effect of the present invention is:
1. do not need metal or metallic compound to make catalyst, products therefrom has very high-purity;
2. growth in situ is with silicon integrated technique compatibility;
3. control the method output height of nanowire growth, cost is low, and is simple to operate.
In addition, at deposited amorphous attitude SiO
xCan mix elements such as B or P in the film, realize the preparation of large-area P type or N type silica/silicon nano wire, very important application prospect be arranged at microelectronics and nano-electron field.
Description of drawings
For further specifying concrete technology contents of the present invention, below in conjunction with embodiment and accompanying drawing describes in detail as after, wherein:
Fig. 1 is a flow chart of the present invention.
Fig. 2 is a large tracts of land nanometer silica line scanning electron microscope image of the present invention.
Fig. 3 is the scanning electron microscope image of control large tracts of land nanometer silica line growth of the present invention.
Specific embodiments
The invention will be further described below in conjunction with embodiment
The present invention is with deposited amorphous attitude SiO
xThe monocrystalline silicon of (0＜X≤2) film places the closed quartz tube reative cell that is filled with the protective gas that flows, and 1～5hrs anneals under 1000～1300 ℃ of temperature.Require airtight quartz ampoule reative cell to vacuumize during the preparation silicon nanowires, in the annealing process, the reative cell vacuum remains on 200～500Torr.Will be during control silica/silicon nanowire growth at amorphous state SiO
xLeave groove with photoetching process and wet etching on (0＜X≤2) film, then annealing.The size of nano wire and the area of growth are by annealing time and temperature control.
See also Fig. 1, Fig. 1 is a flow chart of the present invention, and the control growing method of a kind of large-area preparation silicon dioxide of the present invention or silicon nanowires comprises the steps:
The control growing method of a kind of large-area preparation silicon dioxide or silicon nanowires is characterized in that, comprises the steps:
Step 1: on the monocrystalline silicon piece substrate, deposit one deck noncrystalline membrane with physical vaporous deposition, magnetron sputtering method or chemical vapour deposition technique;
Step 2: use photoetching process and wet etching on the amorphous state silicon oxide film of deposition, leave several microns wide groove, expose monocrystalline substrate;
Step 3: in airtight quartz ampoule reaction chamber, charge into mobile N then
2, Ar or N
2And H
2, Ar and H
2Mist is as protective gas;
Step 4: annealing back vertical trench direction ordering growth on monocrystalline substrate goes out large-area silica/silicon nano wire.
Embodiment
One, SiO
xFilm is in capacitance coupling type ultra high vacuum plasma enhanced chemical vapor deposition (PECVD) system, with SiH
4(concentration 15%, Ar dilution) and N
2O is a reacting gas, prepares at (100) Si sheet of handling through RCA.System response initial vacuum 1 * 10
-5Torr, pressure 110mtorr in the reaction, 200 ℃ of underlayer temperatures.Adjust SiH
4And N
2O flow-rate ratio 50/5, radio-frequency power 50W, growth time 30min deposits SiO on the single crystalline Si substrate
0.94Noncrystalline membrane.
Two, be heating source with the tubular horizontal resistance furnace, in airtight quartz ampoule reative cell, charge into mobile N
2/ H
2Mist is as protective gas, and its flow is respectively 500sccm and 25sccm, and the 2hrs that anneals under 1150 ℃ of temperature is at deposited amorphous attitude SiO
0.94Obtain the above large-area nanometer silica line of 10mm * 10mm on the monocrystalline substrate of film, the diameter of its nano wire is about 50nm (consulting Fig. 2);
Three, be heating source with the tubular horizontal resistance furnace, in airtight quartz ampoule reative cell, be evacuated, charge into mobile N during annealing
2And H
2Mist is as protective gas, and its flow is respectively 500sccm and 25sccm, the 2hrs that under 1150 ℃ of temperature, anneals, and the reative cell vacuum remains on 300Torr.At deposited amorphous attitude SiO
0.94Obtain large-area silicon nanowires on the monocrystalline substrate of film, the diameter of its nano wire is about 50nm;
Four, at deposited amorphous attitude SiO
0.94The monocrystalline silicon piece gluing photoetching of film forms the mask of the wide groove of 5 μ m, with hydrofluoric acid cushioning liquid corrosion SiO
0.94Film, till monocrystalline substrate is exposed at definite groove place, the deposition SiO that wet etching is crossed then
0.94It is in the airtight quartz ampoule reative cell of heating source that the monocrystalline silicon piece of film places with the tubular horizontal resistance furnace, charges into mobile N
2And H
2Mist is as protective gas, and its flow is respectively 500sccm and 25sccm, the 1h that under 1150 ℃ of temperature, anneals, and vertical trench direction ordering growth goes out large-area nanometer silica line on the monocrystalline silicon baseplane; When the growth of control silicon nanowires, require airtight quartz ampoule reative cell to vacuumize, in the annealing process, the reative cell vacuum remains on 300Torr, and vertical trench direction ordering growth goes out large-area silicon nanowires (consulting Fig. 3) on the monocrystalline silicon baseplane.
Claims (6)
1. the control growing method of large-area preparation silicon dioxide or silicon nanowires is characterized in that, comprises the steps:
Step 1: on the monocrystalline silicon piece substrate, deposit one deck noncrystalline membrane with physical vaporous deposition, magnetron sputtering method or chemical vapour deposition technique;
Step 2: use photoetching process and wet etching on the amorphous state silicon oxide film of deposition, leave several microns wide groove, expose monocrystalline substrate;
Step 3: in airtight quartz ampoule reaction chamber, charge into mobile N then
2, Ar or N
2And H
2, Ar and H
2Mist is as protective gas;
Step 4: annealing back vertical trench direction ordering growth on monocrystalline substrate goes out large-area silica/silicon nano wire.
2. the control growing method of large-area preparation silicon dioxide according to claim 1 or silicon nanowires is characterized in that, wherein the thickness of noncrystalline membrane is 10～600nm, and noncrystalline membrane is SiO
xThe material of 0＜X≤2 wherein.
3. large-area preparation silicon dioxide according to claim 1 or silicon nanowires control growing method is characterized in that wherein the flow of protective gas is 50～500sccm.
4. large-area preparation silicon dioxide according to claim 1 or silicon nanowires control growing method is characterized in that, annealing temperature wherein is under 1000～1300 ℃ of temperature, and the time is 1～5hrs.
5. large-area preparation silicon dioxide according to claim 1 or silicon nanowires control growing method, it is characterized in that, the large-area silica/silicon nano wire that wherein grows on monocrystalline substrate is of a size of 10mm * 10mm, the diameter of its nano wire is at 20～100nm, and length surpasses 100 μ m.
6. large-area preparation silicon dioxide according to claim 1 or silicon nanowires control growing method is characterized in that, wherein during grow silicon nanowires, the reative cell vacuum remains on 200～500Torr.
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| CN100375235C true CN100375235C (en) | 2008-03-12 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101337654B (en) * | 2007-07-04 | 2010-04-21 | 中国科学院合肥物质科学研究院 | Micron grade blocky silicone base composite body assembled by silicon oxide or willemite nano-wires and method for preparing same |
| WO2009032413A1 (en) | 2007-08-28 | 2009-03-12 | California Institute Of Technology | Method for reuse of wafers for growth of vertically-aligned wire arrays |
| EP2507842A2 (en) | 2009-11-30 | 2012-10-10 | California Institute of Technology | Three-dimensional patterning methods and related devices |
| WO2011156042A2 (en) | 2010-03-23 | 2011-12-15 | California Institute Of Technology | Heterojunction wire array solar cells |
| US9545612B2 (en) | 2012-01-13 | 2017-01-17 | California Institute Of Technology | Solar fuel generator |
| US9476129B2 (en) | 2012-04-02 | 2016-10-25 | California Institute Of Technology | Solar fuels generator |
| US10026560B2 (en) | 2012-01-13 | 2018-07-17 | The California Institute Of Technology | Solar fuels generator |
| WO2013126432A1 (en) | 2012-02-21 | 2013-08-29 | California Institute Of Technology | Axially-integrated epitaxially-grown tandem wire arrays |
| WO2013152132A1 (en) | 2012-04-03 | 2013-10-10 | The California Institute Of Technology | Semiconductor structures for fuel generation |
| US9553223B2 (en) | 2013-01-24 | 2017-01-24 | California Institute Of Technology | Method for alignment of microwires |
| CN103950932A (en) * | 2014-04-16 | 2014-07-30 | 奇瑞汽车股份有限公司 | Preparation method of high-purity orderly semiconductor silicon nanowire |
| CN106276922B (en) * | 2016-08-10 | 2022-06-10 | 渤海大学 | Cross vertical SiO2Nano-rod and preparation method thereof |
| CN110118806A (en) * | 2019-05-29 | 2019-08-13 | 兰州大学 | Ceramic Tube Type gas sensor and preparation method thereof |
| CN114167599B (en) * | 2021-11-01 | 2023-11-07 | 中山大学 | Image integrated super-structured surface and design method thereof |
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| CN1323051A (en) * | 2001-05-28 | 2001-11-21 | 东南大学 | Prepn of ordered nanometer carbon pipe array on silicon chip |
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| CN1474434A (en) * | 2003-07-25 | 2004-02-11 | 中国科学院上海微系统与信息技术研究 | Method for producing silicon nano wire |
| US20040118698A1 (en) * | 2002-12-23 | 2004-06-24 | Yunfeng Lu | Process for the preparation of metal-containing nanostructured films |
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2005
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323051A (en) * | 2001-05-28 | 2001-11-21 | 东南大学 | Prepn of ordered nanometer carbon pipe array on silicon chip |
| CN1382626A (en) * | 2002-03-15 | 2002-12-04 | 清华大学 | Process for synthesizing nano linear carbon array |
| US20040118698A1 (en) * | 2002-12-23 | 2004-06-24 | Yunfeng Lu | Process for the preparation of metal-containing nanostructured films |
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| Title |
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| Oxide-assisted growth of semiconducting nanowires. Rui-Qin Zhang, Yeshayahu Lifshitz, Shuit-Tong Lee.Advanced Materials,Vol.15 No.7-8. 2003 * |
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