CN108364850A - A kind of preparation method of upright GaAs nano wires - Google Patents
A kind of preparation method of upright GaAs nano wires Download PDFInfo
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- CN108364850A CN108364850A CN201810032745.4A CN201810032745A CN108364850A CN 108364850 A CN108364850 A CN 108364850A CN 201810032745 A CN201810032745 A CN 201810032745A CN 108364850 A CN108364850 A CN 108364850A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/02428—Structure
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
Abstract
The invention discloses a kind of preparation methods of upright GaAs nano wires.The relationship of Ga drops catalyst and Si substrate surface contacts angle and substrate surface oxidated layer thickness is obtained according to YoungShi formula,The present invention is handled Si substrate surfaces using HF acid,Keep Si substrate surfaces roughening,And the oxide layer of Si substrate surfaces is partially removed,This method realizes the processing of Si substrate surfaces by using HF acid the control to surface oxide layer thickness,Regulate and control the contact angle of Ga catalyst droplets and substrate surface by adjusting oxidated layer thickness and coarse surface topography,Ga catalyst droplets and substrate surface are made to have suitable contact angle,It realizes and inhibits multiple twin growth,Enable GaAs nano wire vertical growths,There are multiple twins when solving existing self-catalysis epitaxial growth GaAs nano wires,The direction of growth of nano wire is difficult to control,There are a large amount of inclination nano wires,The problem that limitation GaAs nano wires are applied in the devices,To realize high quality,High-performance GaAs nano-wire devices establish material foundation.
Description
Technical field
The present invention relates to field of semiconductor materials, more particularly to upright in Group III-V semiconductor field of nano material preparation
A kind of preparation method of GaAs nano wires.
Background technology
Nano wire be it is a kind of be limited in nanometer scale in the horizontal, and it is longitudinal there is no limit one-dimentional structure, due to
Two dimension energy level splittings of cross-wise direction, this makes it be shown completely in mechanics, electricity, optics etc. relative to body material
Different property.Meanwhile the axial hetero-junctions with radial direction can be formed in structure design, it itself can also be used as one solely
Vertical device so that this nanostructure becomes a kind of constructing module of very promising nanoscale devices, and becomes and grinds
The hot spot studied carefully.Group III-V semiconductor nano material has in terms of nano-device wide due to unique physical property
Application potential and receive the concern of people.GaAs is one of III-V compound semiconductor material, is direct band-gap semicondictor
Material has the characteristics that the electrical and optical properties that high carrier mobility, effective mass are small, excellent, this makes GaAs nanometers
Line becomes a kind of ideal material for preparing electronic device and opto-electronic device, and GaAs nano wires are in LED, laser, detection at present
Device, solar cell, thermo-electric device etc. obtain extensive research.
GaAs nano wires have developed a series of preparation methods in terms of growth, including chemical vapor deposition (CVD), metal have
Machine object vapor deposition (MOVPE), molecular beam epitaxy (MBE) etc..The preparation of nano-material can generally be divided into from top to bottom and
Two kinds from bottom to top, wherein being to go to array structure institute with allowing constituent atoms automatic order by way of material epitaxy from bottom to top
The low dimensionality of nano-wires structure needed limits so as to avoid technique, and carries out nano-material growth by self-catalysis method and belong to
In one kind from bottom to top.For the GaAs nano wires of self-catalysis growth, basic principle is to deposit Ga elements in substrate surface,
So that substrate surface forms Ga drop beads, and as the collection center of Ga atoms and As atoms, it is further passed through Ga and As,
With the increase of As components in Ga-As alloys and over-saturation state is progressivelyed reach, GaAs is precipitated in interface and forms GaAs and receives
Rice noodles.This self-catalysis mode avoids dissimilar metal pollution nano wire, meanwhile, it is more excellent in terms of the defect for reducing nano wire
Gesture is best suited for the application of extensive nano wire electronics device, is one of nano wire preparation method of most Research Prospects.
Currently, the growth of GaAs nano-materials may be implemented by different growing technologies, in GaAs nano-materials
It is in the majority with self-catalysis growth pattern in technology of preparing, but realize that GaAs nano wires are grown with substrate transverse on substrate, it obtains straight
Vertical GaAs nano wires are a problems existing for self-catalysis epitaxy technology, and self-catalysis grows GaAs nano wires since there are multiple
Twin so that the direction of growth of nano wire is difficult to control, and then a large amount of inclined nano wires occurs, limits nano wire in device
In application.Therefore, the GaAs nano wires for how realizing vertical growth realize that the application of upright GaAs nano wires in the devices is
Primarily solve the problems, such as.
Invention content
The present invention proposes a kind of preparation method of upright GaAs nano wires, this method by with HF acid solutions to Si substrate tables
The natural oxidizing layer in face performs etching, and Si substrates is made to obtain coarse surface topography, is carved to the oxide layer of Si substrate surfaces
Erosion, by handling the control realized to Si substrate surface oxidated layer thickness with HF acid etches, by changing the thickness of oxide layer, and
The contact angle for regulating and controlling Ga catalyst droplets and substrate in conjunction with coarse surface topography makes Ga catalyst droplets and substrate surface
It is final to realize the growth for inhibiting multiple twin with suitable contact angle, make GaAs nano wires perpendicular to substrate vertical growth,
There are multiple twins, the direction of growth of nano wire to be difficult to control when solving existing self-catalysis epitaxy technology growth GaAs nano wires,
There is a large amount of inclined nano wires, the problem that limitation GaAs nano wires are applied in the devices, to realize high quality, high-performance GaAs
Nano-wire devices establish material foundation.
The present invention proposes a kind of preparation method of upright GaAs nano wires, and this method is by controlling Si substrate surface oxide layers
Contact angle with substrate of thickness and coarse surface topography regulation and control Ga catalyst droplets, according to YoungShi formula it is found that lining
Bottom is related with substrate surface oxidated layer thickness with catalyst contact angle, by changing Si liner oxidation layer thickness, by Si substrate oxygen
Change layer to be handled with HF acid etches, it is 0.8nm to make Si surface oxide layer thickness, obtains the GaAs nano wires of vertical-growth.
The present invention proposes a kind of preparation method of upright GaAs nano wires, utilizes HF acid to Si substrate surface oxygen in this method
Change layer processing the specific steps are：1, by HF：H2O is with 1:10 ratio prepares etching liquid, and etching condition is room temperature, in fluorescent lamp
It is performed etching under the environmental condition of irradiation；2, Si substrates are put into prepared etching liquid to the autoxidation of Si substrate surfaces
Layer performs etching, etch period 2s；3, Si substrates are taken out from etching liquid, utilizes ellipsometer measurement surface oxidation tunic
Thickness, when oxidated layer thickness is thicker, etch period is less, when not reaching expected and requiring, Si substrates is put into etching liquid and are continued
Etching, until Si surface oxide layer thickness reaches the present invention and realizes that the 0.8nm thickness required by upright GaAs nanowire growths is wanted
It asks；4, the Si substrates of etching processing are put into the growth that upright GaAs nano wires are carried out in growth apparatus.
The present invention proposes that a kind of preparation method of upright GaAs nano wires, this method grow GaAs with molecular beam epitaxy technique
Nano wire, growth mechanism use the growth pattern of self-catalysis, and catalyst is Ga drops, when Ga drops catalyst is in Si substrate surfaces
When generation, pause 80s keeps Ga drops fully dispersed, to ensure droplet size, to make Ga drops catalyst and pass through HF
For the Si substrate surfaces of acid etch processing there are one suitable surface contact angle, the present invention passes through the natural oxygen to Si substrate surfaces
Changing layer etching keeps Si substrate surfaces roughening, and the thickness of control Si substrate surface oxide layers, realization pair are handled by HF acid etches
The regulation and control of Ga drops and Si substrate surface contacts angle, it is final to realize the GaAs nano wires in molecular beam epitaxial growth GaAs nano wires
The purpose of vertical growth reaches the advantageous effect for preparing upright GaAs nano wires proposed by the invention.
Description of the drawings
Fig. 1 is the technical solution figure that the present invention realizes upright GaAs nanowire preparation methods.
Fig. 2 is upright GaAs nano-materials SEM figures prepared by the present invention.
Specific implementation mode
Below by the drawings and specific embodiments, to the upright GaAs nano-material systems of this realization proposed by the invention
Standby method is described in further detail, and can be prepared and Si substrate transverses using this method proposed by the invention
Upright GaAs nano-materials, prepared upright GaAs nano wires SEM figures are as shown in Fig. 2.
The present invention proposes a kind of preparation method of upright GaAs nano wires, this method by with HF acid solutions to Si substrate tables
The natural oxidizing layer in face performs etching, and keeps Si substrate surfaces roughening, meanwhile, realize the control to Si substrate surface oxidated layer thickness
System, thickness combination Si substrates by changing oxide layer coarse surface topography regulation and control Ga catalyst droplets and substrate surface connect
Feeler degree makes Ga catalyst droplets and substrate surface have suitable contact angle, is finally reached the growth for inhibiting multiple twin,
The vertical-growth for realizing GaAs nano wires, there are multiple twin when solving existing self-catalysis epitaxy technology growth GaAs nano wires,
The direction of growth of nano wire is difficult to control, and a large amount of inclined nano wires, the difficulty that limitation GaAs nano wires are applied in the devices occurs
Topic, to realize that high quality, high-performance GaAs nano-wire devices establish material foundation.It is below Si (111) substrate with substrate, growth
Technology is molecular beam epitaxy technique, and source material used is the sources Ga, the sources As, solution used in etching processing Si substrates be HF acid solutions,
Institute's growth material is GaAs nano wires, and such embodiment carries out specific detailed description.
Fig. 1 show the technical solution figure that the present invention realizes upright GaAs nanowire preparation methods, and Si substrates (1) surface has
Natural oxidizing layer (2) performs etching Si substrate surface natural oxidizing layers with HF acid, obtains coarse surface and oxide layer is suitable
The Si substrate surfaces (3) of thickness, making Ga drops catalyst, there are one suitable surfaces with the Si substrate surfaces by the processing of HF acid
Contact angle obtains upright GaAs nano wires (5) when carrying out GaAs nanowire growths.
Fig. 2 show the upright GaAs nano wires SEM figures that epitaxial growth of the present invention obtains, and can see the present invention in figure
Realize the preparation of upright GaAs nano wires.
Realize that the specific implementation step that in the present embodiment prepared by upright GaAs nano-materials is as follows：
Step 1：Si (111) substrate cleaning treatment, first, by HF：H2O is with 1:10 ratio prepares etching liquid, etches item
Part is room temperature, is etched under daylight light irradiation environment, and then, Si substrates are put into prepared etching liquid to Si substrate surfaces
Natural oxidizing layer perform etching, etch period 2s takes out Si substrates after the HF acid etches of 2s from etching liquid, profit
It, will when the thicker etch period of oxidated layer thickness is less not reached expected and require with ellipsometer measurement surface oxide layer film thickness
Si substrates, which are put into etching liquid, to be continued to etch, until Si substrate surface oxidated layer thickness reaches the present invention and realizes upright GaAs nanometers
The required 0.8nm thickness requirements of line growth are finally ultrasonically treated 5min with absolute ethyl alcohol to the Si substrates after HF acid etches,
It is rinsed well with deionized water (DI) after ultrasonic cleaning processing and is dried up with nitrogen, complete the processing work to Si (111) substrate
Skill can carry out the growth of upright GaAs nano wires；
Step 2：The Si of cleaning treatment (111) substrate is handled in molecular beam epitaxy system, after preliminary treatment
Si (111) substrate be put on the sample carrier of molecular beam epitaxy (MBE) system Sample Room guide rail trolley, Sample Room take out true
Vacancy is managed, when Sample Room vacuum environment is better than 10-8When Torr, the baking temperature of Si substrates is set as 200 DEG C, baking time 2 is small
When, sample is sent into surge chamber by the preliminary aqueous vapor and foreign gas for removing Si substrate surfaces after Sample Room preliminary treatment
(Buffer) in, 350 DEG C of bakings are carried out to Si substrates, baking time 2 hours further removes the gas of Si substrate surface difficulties removal
Body impurity, finally by treated, Si substrates are sent into the growth rooms MBE, wait for GaAs nanowire growths parameter setting and growth source stove
The epitaxial growth of GaAs nano-materials is carried out after parameter stability；
Step 3：The growth of upright GaAs nano wires, growth flow are：First, energetic reflection electron diffraction instrument is opened
(RHEED) in-situ monitoring is carried out to substrate surface, underlayer temperature is added to 620 DEG C, open Ga source valve 10s, deposition Ga catalysis
Agent, subsequent intermediate hold 80s, keeps Ga drops fully dispersed, to ensure droplet size, to make Ga drops catalyst and warp
The Si substrate surfaces of HF acid etches processing are crossed there are one suitable surface contact angle, this suitable surface contact angle can be with
Realize that the vertical growth of GaAs nano wires, GaAs nanowire growth temperatures are 620 DEG C, Ga source oven temperature degree is 995 DEG C, corresponding Ga
Line equivalent pressure is 6.2 × 10-8Torr, As source oven temperature degree are 600 DEG C, and corresponding As lines equivalent pressure is 1.6 × 10- 6Torr, As/Ga line ratio are 25.8, growth time 10min, and epitaxial growth with this condition obtains GaAs nano-materials；
Step 4：After the growth for completing GaAs nano wires, the sources Ga, the sources As flapper closure, source oven temperature degree cooling, when substrate temperature
Degree closes the sources As after being less than 400 DEG C, and after waiting for epitaxial device parameter to reach arrange parameter, growth is had upright GaAs nano wires
Si substrates are transmitted and are taken out by guide rail trolley, to grow sample surface topography and GaAs nano-materials crystal quality into
Row test characterization, completes the preparation of upright GaAs nano-materials.
A kind of the application preparation method of upright GaAs nano-materials claimed is realized by above step, it should
Method makes Si substrates obtain coarse surface shape by being performed etching to the natural oxidizing layer of Si substrate surfaces with HF acid solutions
Looks perform etching the oxide layer of Si substrate surfaces, are handled by HF acid etches, realize the control to Si surface oxide layer thickness
System regulates and controls Ga catalyst droplets and substrate table by the coarse surface topography of the thickness combination Si substrate surfaces of change oxide layer
The contact angle in face makes Ga catalyst droplets and substrate surface have suitable contact angle, this suitably contacts angle can
To realize the growth for inhibiting multiple twin, the vertical-growth of GaAs nano wires is realized, solve existing self-catalysis epitaxy technology growth
There are multiple twins, the direction of growth of nano wire to be difficult to control when GaAs nano wires, a large amount of inclined nano wires, limitation occurs
The problem that GaAs nano wires are applied in the devices, to realize that high quality, high-performance GaAs nano-wire devices establish material foundation.
Claims (5)
1. a kind of preparation method of upright GaAs nano wires, which is characterized in that this method is by using HF acid to Si substrate surfaces
It is handled, keeps Si substrate surfaces roughening, and the oxide layer of Si substrate surfaces is partially removed, Si is being served as a contrast by HF acid
Bottom surface etching processing realizes the purpose controlled Si substrate surface oxidated layer thickness, adjusts Si substrate surface oxidated layer thickness
And the roughness of Si substrate surfaces makes to realize the adjusting of the contact angle to Ga catalyst droplets Yu Si substrate surfaces indirectly
Ga catalyst droplets have suitable contact angle with Si substrate surfaces, realize the growth for inhibiting multiple twin, make GaAs nano wires
Can vertical growth, there are multiple twin, the directions of growth of nano wire when solving existing self-catalysis epitaxial growth GaAs nano wires
It is difficult to control, a large amount of inclination nano wires, the problem that limitation GaAs nano wires are applied in the devices, the Ga drops catalyst occurs
The growth that upright GaAs nano wires may be implemented in angle is suitably contacted between Si substrate surfaces, HF acid described in this method is right
The processing of Si substrate surface natural oxidizing layers completes Si substrate surfaces when the oxidated layer thickness of Si substrate surfaces is 0.8nm certainly
The HF acid etches processing of right oxide layer, the Si substrate surfaces natural oxidizing layer can make Ga liquid when being etched to 0.8nm thickness
Drop catalyst has suitable contact angle with Si substrate surfaces, when carrying out the growth of GaAs nano-materials, Ga catalyst droplets
The growth that angle keeps GaAs nano wires upright is suitably contacted with Si substrate surfaces, the Ga drops catalyst is in Si substrate surfaces
After formation, the 80s of pause 80s, the pause can enable Ga drops fully dispersed, ensure the suitable size of drop, make Ga
There are one suitable surface contact angle, this described conjunctions with the Si substrate surfaces by the processing of HF acid etches for drop catalyst
Suitable surface contact angle realizes the upright growth of GaAs nano wires.
2. a kind of preparation method of upright GaAs nano wires as described in claim 1, which is characterized in that this method utilizes Ga liquid
Drop is used as catalyst, the growth mechanism of self-catalysis to be grown, and Si substrate surfaces are handled using HF acid, makes Si substrate surfaces oneself
Right oxide layer is etched, and the thickness of oxide layer is 0.8nm, Ga liquid after the natural oxidizing layer of Si substrate surfaces is etched in this method
Catalyst is dripped with the Si substrate surfaces of the oxidated layer thickness there are one contact angle, this described contact angle is suitble to GaAs to receive
The upright growth of rice noodles.
3. a kind of preparation method of upright GaAs nano wires as described in claim 1, which is characterized in that served as a contrast to Si using HF acid
Bottom surface oxide layer processing the specific steps are：1, by HF：H2O is with 1:10 ratio prepares etching liquid, and etching condition is room temperature,
It is performed etching under daylight light irradiation environmental condition；2, by Si substrates be put into prepared etching liquid to Si substrate surfaces from
Right oxide layer performs etching, etch period 2s；3, Si substrates are taken out from etching liquid, utilizes ellipsometer measurement Si substrate tables
The oxide layer film thickness in face, when oxidated layer thickness is thicker, etch period is less, and Si substrate surfaces oxidated layer thickness does not reach expected
It is required that when, Si substrates are put into etching liquid and continue to etch, until Si substrate surface oxidated layer thickness reaches realization of the present invention
0.8nm thickness requirements required by GaAs nano wire vertical growths.
4. a kind of preparation method of upright GaAs nano wires as described in claim 1, which is characterized in that carrying out GaAs nanometers
When line is grown, when Ga drops catalyst is when Si substrate surfaces generate, the 80s of pause 80s, pause can enable Ga drops
Enough fully to spread and be in stable state, it is suitable size to make Ga drops, realizes Ga drops catalyst and passes through HF acid etches
There are one suitable surface contact angle, the suitable surface contact angles may be implemented to instruct GaAs for the Si substrate surfaces of processing
Nano wire vertical growth.
5. a kind of preparation method of upright GaAs nano wires as described in claim 1, which is characterized in that by using the present invention
This method proposed, first, performing etching processing to Si substrate surface natural oxidizing layers enables Ga drops catalyst to be served as a contrast with Si
Bottom surface has suitable contact angle, then, when growing GaAs nano wires, stops 80s when Ga drop formations, makes Ga drops
It fully spreads and is in stable state with the contact of Si substrates, finally, carry out nanowire growth, obtain upright GaAs nano wires
Material, when solving existing self-catalysis epitaxial growth GaAs nano wires, there are the directions of growth of multiple twin, nano wire to be difficult to control
System, occur it is a large amount of tilt nano wires, the problem of limitation GaAs nano wires are applied in the devices, method proposed by the invention can be with
Upright high quality GaAs nano-materials are realized, to pushing the improvement of GaAs nano-wire devices performances to establish material foundation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109801835A (en) * | 2018-12-14 | 2019-05-24 | 华南理工大学 | A kind of method of grown at low temperature GaAs nano wire |
| CN109767972B (en) * | 2018-12-13 | 2021-05-14 | 华南理工大学 | Method for growing GaAs nanowire on Si substrate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109767972B (en) * | 2018-12-13 | 2021-05-14 | 华南理工大学 | Method for growing GaAs nanowire on Si substrate |
| CN109801835A (en) * | 2018-12-14 | 2019-05-24 | 华南理工大学 | A kind of method of grown at low temperature GaAs nano wire |
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Application publication date: 20180803 |