CN1302996C - Method for preparing zinc sulfide nanometer thread using ion aided MOCVD apparatus - Google Patents
Method for preparing zinc sulfide nanometer thread using ion aided MOCVD apparatus Download PDFInfo
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- CN1302996C CN1302996C CNB2004100113491A CN200410011349A CN1302996C CN 1302996 C CN1302996 C CN 1302996C CN B2004100113491 A CNB2004100113491 A CN B2004100113491A CN 200410011349 A CN200410011349 A CN 200410011349A CN 1302996 C CN1302996 C CN 1302996C
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Abstract
The present invention belongs to the technical field of a semiconductor material, which relates to a preparation method for a sulfide nanometer line by making use of a plasma auxiliary metal organic chemical vapor deposition method. An alternative electric field is generated by a high-frequency induction coil by making use of the difference of the stability of the polar surface and the non-polar surface of ZnS in a plasma treatment method; thus, an air source is ionized, and the reaction activity is increased. ZnS generated on the surface of a substrate has strong polarity and is easily migrated on the surface to form the initial ZnS nanosphere structure; the ZnS nanosphere structure continues growing to form a ZnS nanometer line. In the preparation method of the present invention, the introduction of a catalyst or a mould plate is not necessary; a ZnS nanometer line array is obtained through oriented growth; no other impurities or forms exist. Nanometer lines with different diameters can be grown out by controlling growth temperature. Consequently, the ZnS nanometer line prepared by the method can be used as an almost ideal material for scientific research, and lays the good foundation for the preparation and the realization of nanometer devices afterwards.
Description
Technical field
The invention belongs to technical field of semiconductor, relate to the preparation of nano material, specifically utilize the auxiliary MOCVD equipment of plasma to prepare the method for sulfide nanometer linear.
Background technology
As one of member of nano material, nano wire becomes the focus of investigation of materials in recent years because of characteristics such as its excellent optical property, electric property and mechanical property have caused the concern of Condensed Matter Physics circle, chemical boundary and material supply section educational circles scientists.ZnS is an a kind of II-VI family wide band gap semiconducter compound, can be used for materials such as flat-panel monitor, electroluminescent device, infrared window.In addition, the ZnS monodimension nanometer material for example: nano wire, nanometer rod and nano belt etc. have all shown the optics and the electrology characteristic of the uniqueness of some different and body materials.At present, both at home and abroad about carrying out rapidly in the research work aspect the low-dimensional ZnS material, nano wire, nanotube, nano-pillar, nano belt etc. all are produced.Though the ZnS nano wire also has report,, show the randomness of orientation owing to be directly deposition rather than epitaxy.These ZnS nano wires generally adopt the method for thermal evaporation of ZnS powder and chemosynthesis.Owing to be subjected to preparation method's restriction.The composition that also has other form in the product that is generated is as nanometer rod and nano particle etc.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the ZnS nano wire that repeatability is excellent, controllability is good with the auxiliary MOCVD equipment of plasma.Utilize the high reactivity of plasma body to increase Zn and S ionic transfer ability, realize the structure again on surface.By the control growing condition, realize the growth of small size (nanometer) linear structure.Need not template or catalyzer, specifically is exactly to have realized utilizing the auxiliary MOCVD of plasma to prepare the method for ZnS nano wire.
Technology of preparing involved in the present invention is the auxiliary metal organic chemical vapor deposition of plasma body (MOCVD).Electric field by an alternation of radio-frequency induction coil generation makes the source of the gas ionization, increases reactive behavior.Therefore, move more intense the generation on the surface easily of ZnS polarity that substrate surface generates, form initial ZnS nanometer ball-like structure, continued growth forms the nano wire of ZnS.
In order more to be expressly understood the present invention in detail, ZnS nano wire preparation process is described in detail below.
At first on the graphite base in the metal organic chemical vapor deposition (MOCVD) growth room, put into cleaned sapphire or Si substrate, under mechanical pump and low pressure controller effect with growth room's pressure-controlling 1.33 * 10
3-2.67 * 10
3Pa, it is 0.3-0.5MHz that the adjusting high frequency induction power supply makes plasma frequency.Can select other substrate for use, other used substrat structure and character and sapphire or Si are similar, and it is better that the material with hexagonal structure is made substrate.When the substrate growth temperature rises to 600-700 ℃, feed high-purity hydrogen by palladium tube purifying 99.999%, to substrate processing 10-20 minute,, feed the hydrogen sulfide H that carries by high-purity hydrogen then successively to remove the impurity of remained on surface
2S, zinc methide DMZn is to the growth room.Hydrogen sulfide H
2The flow of S is 20-40ml/min, and the flow of zinc methide DMZn is 10-20ml/min, and total hydrogen carrier gas is controlled at 2L/min.Be controlled at about-27 ℃ by the temperature of cold-trap device, can under plasma body is assisted, finish the growth of ZnS nano-wire array the Zn source.Growth time is 50-60 minute, and in whole growth process, no template or catalyzer are introduced.
The present invention utilizes the auxiliary metal organic chemical vapor deposition of plasma body to prepare semiconductor material, has the incomparable advantage of other growth method, is the preferred approach that realizes research and fabricate devices.Need not to introduce catalyzer or template, get final product the ZnS nano wire that oriented growth goes out better quality.According to ZnS polar surface and non-polar plane stability relationship, directly,, obtained the ZnS nano-wire array not by means of template or catalyzer by regulating the effect of plasma body intermediate ion and ZnS, there are not other impurity and form, as nano particle and nanometer sheet etc.Can grow the nano wire of different diameter by the control growing temperature.Therefore, the ZnS nano wire of preparing in this way can be used as a kind of near ideal scientific research material, for the preparation and the realization of nano-device later on had laid a good foundation.
So, utilize the auxiliary MOCVD equipment of this plasma to need not to adopt any catalyzer for the growth of one-dimensional nano structure.In addition, the MOCVD equipment manufacturing cost is cheap, and is easy to operate, is suitable for large-scale production again.
Embodiment
Embodiment 1, and growth diameter is about the nano wire of 100nm on sapphire and silicon substrate.
Adopt metal organic chemical vapor deposition (MOCVD) equipment of oneself assembling, at first cleaned sapphire and Si substrate, be placed on the graphite base in the metal organic chemical vapor deposition (MOCVD) growth room, under mechanical pump and low pressure controller effect with growth room's pressure-controlling 2.13 * 10
3Pa, it is 0.3MHz that the adjusting high frequency induction power supply makes plasma frequency.When the substrate growth temperature rises to 600 ℃, feed high-purity hydrogen, to substrate processing 10-20 minute by palladium tube purifying 99.999%.Feed the hydrogen sulfide H that carries by high-purity hydrogen then successively
2S, its flow are 30ml/min, and the flow of zinc methide DMZn is 15ml/min, to the growth room.Total hydrogen carrier gas is controlled at 2L/min.By the cold-trap device temperature in Zn source is controlled at-27 ℃, growth time is 50 minutes, and in whole growth process, no template or catalyzer are introduced.
The flow of zinc source and the carrier gas of sulphur source is respectively 1200ml/min,, 600ml/min, high-frequency induction voltage is 2.5KV.
Utilize the present invention, on sapphire, silicon substrate, prepared the ZnS nano wire that diameter is about 100nm.The X-ray diffraction measurement shows to grow to have the ZnS nano wire of preferred orientation for (002) direction on substrate.The high about 250-300 nanometer of single nano wire, about 100 nanometers of diameter.
Embodiment 2, and growth diameter is about the nano wire of 25-30nm on sapphire and silicon substrate.
Adopt metal organic chemical vapor deposition (MOCVD) equipment of oneself assembling, at first cleaned sapphire and Si substrate, be placed on the graphite base in the metal organic chemical vapor deposition (MOCVD) growth room, under mechanical pump and low pressure controller effect with growth room's pressure-controlling 1.33 * 10
3Pa, it is 0.3MHz that the adjusting high frequency induction power supply makes plasma frequency.When the substrate growth temperature rises to 700 ℃, feed high-purity hydrogen, to substrate processing 10-20 minute by palladium tube purifying 99.999%.Feed the hydrogen sulfide H that carries by high-purity hydrogen then successively
2S, its flow are 30ml/min, and the flow of zinc methide DMZn is 15ml/min, to the growth room.Total hydrogen carrier gas is controlled at 2L/min.By the cold-trap device temperature in Zn source is controlled at-27 ℃, growth time is 50 minutes, and in whole growth process, no template or catalyzer are introduced.
The flow of zinc source and the carrier gas of sulphur source is respectively 1200ml/min,, 600ml/min, high-frequency induction voltage is 3.5KV.
Utilize the present invention, on sapphire, silicon substrate, prepared the ZnS nano wire that diameter is about 25-30nm.The X-ray diffraction measurement shows to grow to have the ZnS nano wire of preferred orientation for (002) direction on substrate.The high about 200-300 nanometer of single nano wire, diameter is about the nano wire of 25-30nm.Light at room temperature photoluminescence stave is bright have been obtained stronger free exciton emission peak and the glow peak blue shift phenomenon that quantum size effect causes occurred.
Embodiment 3, growing nano ball on sapphire and silicon substrate.
Adopt metal organic chemical vapor deposition (MOCVD) equipment of oneself assembling, at first cleaned sapphire and Si substrate, be placed on the graphite base in the metal organic chemical vapor deposition (MOCVD) growth room, under mechanical pump and low pressure controller effect with growth room's pressure-controlling 1.33 * 10
3Pa, it is 0.3MHz that the adjusting high frequency induction power supply makes plasma frequency.When the substrate growth temperature rises to 700 ℃, feed high-purity hydrogen, to substrate processing 10-20 minute by palladium tube purifying 99.999%.Feed the hydrogen sulfide H that carries by high-purity hydrogen then successively
2S, its flow are 30ml/min, and the flow of zinc methide DMZn is 15ml/min, to the growth room.Total hydrogen carrier gas is controlled at 2L/min.By the cold-trap device temperature in Zn source is controlled at-27 ℃, growth time is 10 minutes, and in whole growth process, no template or catalyzer are introduced.
The flow of zinc source and the carrier gas of sulphur source is respectively 1200ml/min,, 600ml/min, high-frequency induction voltage is 3.5KV.
In order to study the growth mechanism of nano wire, the nano wire that utilizes the present invention on sapphire and silicon substrate, to grow 10 minutes.Find to be uniform-distribution with the nanometer ball that some diameters are 25-30nm on substrate by scanning electronic microscope (SEM), the diameter of ball is identical with the diameter of line, and these nanometer balls are summed up as the initial nucleation of nano wire.
Claims (6)
1, a kind of method for preparing sulfide nanometer linear with the auxiliary MOCVD equipment of plasma, it is characterized in that: at first be on metal organic chemical vapor deposition (MOCVD) growth room heating base, to put into cleaned sapphire and silicon substrate, make growth room's pressure-controlling 1.33 * 10 by mechanical pump and low pressure controller
3-2.67 * 10
3Pa, applying high frequency induction power supply again, to make plasma frequency be 0.3-0.5MHz; When the substrate growth temperature rises to 600-700 ℃, feed high-purity hydrogen by the palladium tube purifying, feed the hydrogen sulfide H that high-purity hydrogen carries then successively
2S, zinc methide DMZn; By the cold-trap device temperature in Zn source is controlled at-27 ℃, under plasma body is assisted, finishes the growth of ZnS nano wire.
2, according to claim 1ly prepare the method for sulfide nanometer linear with the auxiliary MOCVD equipment of plasma, the flow that it is characterized in that zinc methide DMZn is 10-20ml/min, H
2The S gas flow is 20-40ml/min, and total hydrogen carrier gas is controlled at 2L/min.
3, according to claim 2ly prepare the method for sulfide nanometer linear, it is characterized in that the flow of zinc source and the carrier gas of sulphur source is respectively: 1200ml/min, 600ml/min with the auxiliary MOCVD equipment of plasma.
4, according to claim 3ly prepare the method for sulfide nanometer linear, it is characterized in that growth room's pressure-controlling is 2.13 * 10 with the auxiliary MOCVD equipment of plasma
3Pa, growth temperature is 600 ℃, the flow of zinc methide DMZn is 15ml/min, H
2The S gas flow is 30ml/min, and the flow of zinc source and the carrier gas of sulphur source is respectively: 1200ml/min, 600ml/min, growth time are 50 minutes.
5, according to claim 3ly prepare the method for sulfide nanometer linear, it is characterized in that growth room's pressure-controlling is 1.33 * 10 with the auxiliary MOCVD equipment of plasma
3Pa, growth temperature is 700 ℃, the flow of zinc methide DMZn is 15ml/min, H
2The S gas flow is 30ml/min, and the flow of zinc source and the carrier gas of sulphur source is respectively: 1200ml/min, 600ml/min, growth time are 50 minutes.
6, according to claim 3ly prepare the method for sulfide nanometer linear, it is characterized in that growth room's pressure-controlling is 1.33 * 10 with the auxiliary MOCVD equipment of plasma
3Pa, growth temperature is 700 ℃, the flow of zinc methide DMZn is 15ml/min, H
2The S gas flow is 30ml/min, and the flow of zinc source and the carrier gas of sulphur source is respectively: 1200ml/min.600ml/min, growth time are 10 minutes.
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CN116462188A (en) * | 2023-05-11 | 2023-07-21 | 清华大学 | Method for improving purity of carbon nano tube, carbon nano tube and application |
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CN1396300A (en) * | 2002-07-17 | 2003-02-12 | 清华大学 | Process for preparing large-area zinc oxide film with nano lines by physical gas-phase deposition |
CN1526644A (en) * | 2003-09-19 | 2004-09-08 | 中国科学院上海硅酸盐研究所 | Wet chemical process of preparing nano zinc oxide wire |
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CN1396300A (en) * | 2002-07-17 | 2003-02-12 | 清华大学 | Process for preparing large-area zinc oxide film with nano lines by physical gas-phase deposition |
CN1526644A (en) * | 2003-09-19 | 2004-09-08 | 中国科学院上海硅酸盐研究所 | Wet chemical process of preparing nano zinc oxide wire |
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