CN102515251A - Preparation method of dodecagonal zinc oxide micron rod - Google Patents
Preparation method of dodecagonal zinc oxide micron rod Download PDFInfo
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- CN102515251A CN102515251A CN2011104437610A CN201110443761A CN102515251A CN 102515251 A CN102515251 A CN 102515251A CN 2011104437610 A CN2011104437610 A CN 2011104437610A CN 201110443761 A CN201110443761 A CN 201110443761A CN 102515251 A CN102515251 A CN 102515251A
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Abstract
The invention discloses a method for preparing a dodecagonal zinc oxide micron rod. The method carries out secondary growth by integrating a hydrothermal method and a gas phase transmission method, and comprises the following steps that: first, a hexagonal zinc oxide micron rod is prepared through the hydrothermal method; then secondary epitaxial growth is carried out through the gas phase transmission method; and in the gas phase transmission method, because the side atoms of the hexagonal zinc oxide micron rod are desorbed, a cross sectional structure turns from a hexagon to a dodecagon. The method is simple and easy to operate, has low manufacturing cost, and can realized controlled preparation. The dodecagonal zinc oxide micron rod can be applied in designing an ultraviolet micro-laser with ultra-high quality factors and an ultra-low threshold.
Description
Technical field
The present invention's design provides the secondary growth preparation method of realizing the dodecagon zinc oxide micron rods; This method at first utilizes hydrothermal reaction at low temperature to prepare the hexagon zinc oxide micron rods; Next utilizes High Temperature Gas phase transmission method on acquired hexagon micron bar, to carry out the secondary epitaxy growth; Utilize atomic adsorption-desorption kinetics and smooth surface behavior in the crystal growing process, realize that zinc oxide hexagon micron bar changes dodecagon gradually into.The present invention is designed to make up the method that high-quality microcavity optical crystal provides a kind of simple and stable.
Background technology
Since 1997 Japan and Hong Kong scientist in the zinc oxide films film system, observed ultraviolet laser radiation first, the research of zinc oxide material has attracted numerous investigators' interest.In last decade, the preparation of zinc oxide micron/nano structure and characteristic research thereof obtain many achievements that attract people's attention, and people utilize different preparation to obtain abundant zinc oxide micron/nano structure, and its optical phenomena has been carried out deep research.Calendar year 2001 U.S.'s University of California scientist on Science reported first the Fabry-Perot pattern ultraviolet laser radiation in the zinc oxide nanowire, thereby disclosed the application prospect of zinc oxide micron/nano structure at ultraviolet micro laser and low-light source domain.The researchist of Leipzig, Germany university in 2008 utilizes a kind of novel echo wall die micro laser of the creationary structure of regular hexagonal section structure of zinc oxide micron rods; Thereby this micro laser utilizes light path to form Echo Wall module lasing in the inner total reflection of regular hexagon microcavity; Light can be formed optical circuit by the cavity inner wall total reflection in this case; Therefore optical loss is extremely faint, so the echo wall die laser radiation in the zinc oxide micron rods is higher than the Fabry-Perot lasor radiation quality factor in the zinc oxide nanowire.
Traditional echo wall die micro laser all is to have adopted circular optical crystal micro-cavity structure; Because the optics restriction ability of circular microcavity is the strongest; And boundary losses is minimum; Yet circular microcavity is difficult to direct acquisition, and we utilize the micro-machined method of photoetching to obtain circular microcavity usually, but little course of processing can't realize the smooth enough circular optical crystal microcavity in border.The wurtzite structure characteristic of zinc oxide material has determined zinc oxide micron/nano structure all to have the regular hexagonal section structure usually, yet the regular hexagon microcavity is not optimal echo wall die microcavity.More approach circular zinc oxide micron/nano structure if can prepare, then can realize the echo wall die micro laser of and lower threshold value more high-quality than regular hexagon zinc oxide micro laser, this will advance the application of zinc oxide aspect Echo Wall micro laser.
Based on above research background introduction, on the basis of original preparation hexagon zinc oxide micron/nano structure, realizing more approaching circular dodecagon zinc oxide microstructure will have great importance.Therefore this patent has been announced a kind of preparation dodecagon zinc oxide micron rods method; The acquisition dodecagon zinc oxide micron rods of this method ability controllability; And the border is smooth, can to greatest extent light be constrained in the zinc oxide cavity, thereby realize high-quality echo wall die laser radiation.
Summary of the invention
Technical problem: the present invention provides a kind of method that effectively repeatably prepares the dodecagon zinc oxide micron rods; Through regulation and control to reactant concn and time; The size of dodecagon zinc oxide micron rods be can effectively regulate and control, thereby the quality factor and the lasing threshold of echo wall die laser radiation in this structure of regulation and control reached.
Technical scheme: in the present invention, in conjunction with hydrothermal reaction at low temperature and High Temperature Gas mutually transmission method carry out diauxic growth, thereby obtain dodecagon zinc oxide micrometer bar structure.
The present invention adopts following technical scheme:
The first step: cutting substrate high preferred orientation is the surface finish silicon chip substrate of (100), utilizes ultrasonic to the silicon chip substrate cleaning surfaces.
Second step: compound concentration is acetate dihydrate zinc solution and the hexamethylenetetramine solution of 0.02mol/L～0.05mol/L.1: 1 by volume with in acetate dihydrate zinc solution and the hexamethylenetetramine solution mixing back injection Teflon autoclave.
The 3rd step: silicon chip substrate cleaned in the first step is inserted in the reaction kettle that is full of solution, kept the silicon chip substrate polished surface down.The sealed high pressure reaction kettle is then inserted autoclave in 85 ℃～90 ℃ baking ovens in the TR, and the reaction times is set to 4 to 6 hours.Reaction finishes the back and takes out silicon chip substrate, utilizes deionized water to wash this sample repeatedly to remove zinc oxide micron rods and the residual reaction soln of silicon chip surface, subsequently this sample is inserted in 90 ℃ the baking oven, dry 10 minutes, with the deionized water of removal remained on surface.
The 4th step: with purity be 99.99% Zinc oxide powder and carbon dust mixed in 1: 1 in molar ratio the back fully grinding insert in the ceramic boat.The ceramic boat that the reaction source material is housed is positioned over the test tube bottom, the 3rd sample of handling well placed test tube middle distance ceramic boat 20cm place.Test tube is pushed in the tube furnace, make ceramic boat be positioned at 850 ℃～950 ℃ humidity provinces, make sample substrate be positioned at 650 ℃～700 ℃ humidity provinces through temperature controlling system.
The 5th step: after accomplishing for the 4th step, in tube furnace, feed 5～10sccm oxygen and 85～100sccm argon gas, connect the tube furnace vacuum system, air pressure is 10～15Pa in the maintenance tube furnace.
The 6th step: react after 20～30 minutes; Close vacuum system, stop aerating oxygen and argon gas after, open tube furnace; After therefrom directly taking out sample substrate sample is characterized, can find that original hexagon zinc oxide micron rods changes the dodecagon micron bar into.
Beneficial effect: compared with prior art, the present invention has the following advantages:
1. the zinc oxide echo wall die microcavity of having reported is the regular hexagon microcavity, and the zinc oxide of this patent method preparation has the dodecagon microcavity, and its quality factor is higher.
2. the present invention has avoided the complex process that etching method prepares Echo Wall microcavity laser cavity; Utilize the gas phase transmission method to carry out the dodecagon zinc oxide micron rods that the secondary epitaxy growth obtains, crystal mass is high, and the border is smooth; Help the total reflection of light in the cavity, thereby improve quality factor.
3. the dodecagon zinc oxide micron rods diameter of the present invention preparation can be regulated through the control to reactant concn, so the zlasing mode of micro-cavity laser and optical maser wavelength are adjustable.
Description of drawings
Fig. 1 Hydrothermal Preparation device synoptic diagram,
Fig. 2 gas phase transmission method carries out diauxic growth device synoptic diagram.
Embodiment
The first step: cutting substrate high preferred orientation is the surface finish silicon chip of (100), and each silicon chip substrate of cutting back is of a size of 3*4cm.At acetone soln, ethanol easily and in the deionized water ultrasonic successively 5 minutes makes the silicon chip substrate cleaning surfaces with these rectangle chip substrates.
Second step: compound concentration is acetate dihydrate zinc solution and the hexamethylenetetramine solution of 0.02mol/L～0.05mol/L respectively; Utilize magnetic agitation at room temperature to stir 2 hours, make the fully dissolving in deionized water solution of zinc acetate dihydrate and hexamethylenetetramine.Then distinguish 1: 1 by volume acetate dihydrate zinc solution and hexamethylenetetramine solution are mixed, get in the Teflon autoclave that 80ml mixing solutions injection capacity is 80ml.
The 3rd step: silicon chip cleaned in the first step is inserted in the reaction kettle that is full of solution, keep silicon wafer polishing face down (as shown in Figure 1).The sealed high pressure reaction kettle; Then autoclave is inserted temperature and is set in 85 ℃～90 ℃ baking ovens in the scope; Reaction times is set to 4 to 6 hours, and reaction is taken out silicon chip after finishing immediately from reaction kettle, and zinc oxide micron rods promptly is grown on the silicon wafer polishing face.Utilize deionized water to wash this sample repeatedly, subsequently this sample is inserted in 90 ℃ the baking oven, dry 10 minutes, with the deionized water of removal remained on surface to remove zinc oxide micron rods and the residual reaction soln of silicon chip surface.Utilize the surface sweeping electron microscope to this sample characterization, the diameter of zinc oxide micron rods is about 5 microns in this sample, and length is about 15 microns.
The 4th step: purity is 99.99% Zinc oxide powder and carbon dust fully grinding of mixing back in 1: 1 in molar ratio, above-mentioned abrasive flour is inserted in the ceramic boat as reaction source.Ceramic boat length 2cm, width 1cm, degree of depth 1cm.The ceramic boat that 0.5g reaction source material is housed is positioned over the test tube bottom of diameter 3.5cm length 30cm, the 3rd sample substrate of handling well placed apart from 10cm place, test tube split shed place, promptly sample substrate is apart from reaction source material downstream 20cm.When packing sample substrate into, that surface of the hexagon zinc oxide micron rods that keeps having grown can guarantee the growth of hexagon zinc oxide micrometer generation secondary epitaxy down like this.This test tube is pushed in the tube furnace, make ceramic boat be positioned at 850 ℃～950 ℃ humidity provinces, make sample substrate be positioned at slightly low temperature and locate for 650 ℃～700 ℃ through temperature controlling system.Fig. 2 is this step reaction device synoptic diagram.
The 5th step: after accomplishing for the 4th step, in tube furnace, feed 5～10sccm oxygen and 85～100sccm argon gas, connect the tube furnace vacuum system, air pressure is 10～15Pa in the maintenance tube furnace.
The 6th step: react after 20～30 minutes; Close vacuum system, stop aerating oxygen and argon gas after, open tube furnace; After therefrom directly taking out sample substrate sample is characterized, can find that original hexagon zinc oxide micron rods changes the dodecagon micron bar into.
Claims (1)
1. the preparation method of a dodecagon zinc oxide micron rods is characterized in that this preparation method is specific as follows:
The first step: cutting substrate high preferred orientation is the surface finish silicon chip substrate of (100), utilizes ultrasonic to the silicon chip substrate cleaning surfaces;
Second step: compound concentration is acetate dihydrate zinc solution and the hexamethylenetetramine solution of 0.02mol/L～0.05mol/L, and 1: 1 by volume with in acetate dihydrate zinc solution and the hexamethylenetetramine solution mixing back injection Teflon autoclave;
The 3rd step: silicon chip substrate cleaned in the first step is inserted in the reaction kettle that is full of solution, kept the silicon chip substrate polished surface down; The sealed high pressure reaction kettle, then autoclave is inserted temperature and is set in 85 ℃～90 ℃ the baking oven, and the reaction times is set to 4 to 6 hours; Reaction finishes the back and takes out silicon chip substrate, utilizes deionized water to wash this sample repeatedly to remove zinc oxide micron rods and the residual reaction soln of silicon chip surface, subsequently this sample is inserted in 90 ℃ the baking oven, dry 10 minutes, with the deionized water of removal remained on surface;
The 4th step: with purity be 99.99% Zinc oxide powder and carbon dust mixed in 1: 1 in molar ratio the back fully grinding insert in the ceramic boat; The ceramic boat that the reaction source material is housed is positioned over the test tube bottom, the 3rd sample of handling well placed test tube middle distance ceramic boat 20cm place; Test tube is pushed in the tube furnace, make ceramic boat be positioned at 850 ℃～950 ℃ humidity provinces, make sample substrate be positioned at slightly low temperature and locate for 650 ℃～700 ℃ through temperature controlling system;
The 5th step: after accomplishing for the 4th step, in tube furnace, feed 5～10sccm oxygen and 85～100sccm argon gas, connect the tube furnace vacuum system, air pressure is 10～15Pa in the maintenance tube furnace;
The 6th step: react after 20～30 minutes; Close vacuum system, stop aerating oxygen and argon gas after, open tube furnace; After therefrom directly taking out sample substrate sample is characterized, can find that original hexagon zinc oxide micron rods changes the dodecagon micron bar into.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948101A (en) * | 2016-04-22 | 2016-09-21 | 西安交通大学 | Corrugated ZnO nanorod and preparation method thereof |
| CN114045521A (en) * | 2021-11-22 | 2022-02-15 | 北京大学深圳研究生院 | Preparation method of nano-scale electrocatalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100101939A1 (en) * | 2008-10-24 | 2010-04-29 | National Taiwan University | Method For Preparing Zinc Oxide Nano Rod Substrate |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100101939A1 (en) * | 2008-10-24 | 2010-04-29 | National Taiwan University | Method For Preparing Zinc Oxide Nano Rod Substrate |
Non-Patent Citations (3)
| Title |
|---|
| J.DAI, ET AL.: "Exciton and electron-hole plasma lasing in ZnO dodecagonal whispering-gallery-mode microcavities at room temperature", 《APPLIED PHYSICS LETTERS》, vol. 97, no. 1, 6 July 2010 (2010-07-06) * |
| 孙天军: "氧化锌微/纳米材料的气相合成与表征", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, 15 May 2008 (2008-05-15) * |
| 许磊等: "氧化锌纳米棒的低温水溶液化学制备研究", 《华北水利水电学院学报》, vol. 28, no. 4, 31 August 2007 (2007-08-31), pages 97 - 99 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948101A (en) * | 2016-04-22 | 2016-09-21 | 西安交通大学 | Corrugated ZnO nanorod and preparation method thereof |
| CN114045521A (en) * | 2021-11-22 | 2022-02-15 | 北京大学深圳研究生院 | Preparation method of nano-scale electrocatalyst |
| CN114045521B (en) * | 2021-11-22 | 2022-10-28 | 北京大学深圳研究生院 | Preparation method of nano-scale electrocatalyst |
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