CN109119327A - The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate - Google Patents

The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate Download PDF

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Publication number
CN109119327A
CN109119327A CN201810973406.6A CN201810973406A CN109119327A CN 109119327 A CN109119327 A CN 109119327A CN 201810973406 A CN201810973406 A CN 201810973406A CN 109119327 A CN109119327 A CN 109119327A
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China
Prior art keywords
nano
sapphire substrate
epitaxial growth
graphene
aluminium nitride
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CN201810973406.6A
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Chinese (zh)
Inventor
刘忠范
陈召龙
高鹏
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Peking University
Beijing Graphene Institute BGI
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Peking University
Beijing Graphene Institute BGI
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Priority to CN201810973406.6A priority Critical patent/CN109119327A/en
Publication of CN109119327A publication Critical patent/CN109119327A/en
Priority to PCT/CN2019/092806 priority patent/WO2020038103A1/en
Pending legal-status Critical Current

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02518Deposited layers
    • H01L21/02521Materials
    • H01L21/02538Group 13/15 materials
    • H01L21/0254Nitrides
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02365Forming inorganic semiconducting materials on a substrate
    • H01L21/02656Special treatments
    • H01L21/02658Pretreatments
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26Materials of the light emitting region
    • H01L33/30Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The present invention provides a kind of method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate, comprising: deposits graphene layer on the surface of nano-patterned sapphire substrate;Corona treatment is carried out to the graphene layer;And the epitaxial growth aln layer on the graphene layer after processing.The present invention is using graphene nano graphical sapphire substrate as the substrate of aluminium nitride epitaxial growth, and corona treatment is carried out to graphene layer, by means of graphene as buffer layer, utilize the property of Van der Waals extension, high stress caused by lattice mismatch and thermal mismatching and high dislocation density can be reduced, to effectively promote the quality of epitaxial nitride aluminium film.

Description

The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate
Technical field
The present invention relates to Material Fields, in particular to one kind epitaxial growth aluminium nitride on nano-patterned sapphire substrate Method.
Background technique
Aluminium nitride (AlN) is a kind of III-V semiconductor with wide direct band gap, have high heat conductance, high mechanical strength, The properties such as high chemical stability and strong Radiation hardness are answered in photoelectron, high temperature high power device and high-frequency wideband communication device There is wide prospect with aspect.Nano-patterned sapphire substrate is a kind of novel nitride epitaxial substrate, and light can be improved and mention Take efficiency.
Aluminium nitride film is the core base material of ultraviolet LED, but aluminium nitride and nano patterning sapphire epitaxial substrate Between there are huge lattice mismatch and thermal mismatchings, lead to the aluminium nitride film poor quality of epitaxial growth.Moreover, aluminium atom, Nitrogen-atoms migration rate will be far below plane sapphire substrate in patterned substrate, difficult by changing the modes such as pressure, air-flow To obtain smooth aluminium nitride film.Therefore, how effectively to buffer between aluminium nitride and sapphire epitaxial substrate that there are huge crystalline substances Lattice mismatch and thermal mismatching increase aluminium atom, nitrogen-atoms migration rate, so that the quality of aluminium nitride film is promoted, it is ultraviolet to being promoted The performance of LED has great importance.
Summary of the invention
The method of the object of the present invention is to provide a kind of on nano-patterned sapphire substrate epitaxial growth aluminium nitride, has There are huge lattice mismatch and thermal mismatchings between effect buffering aluminium nitride and sapphire epitaxial substrate, increase aluminium atom, nitrogen-atoms Migration rate.
To achieve the above object, scheme of the present invention are as follows:
The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate, comprising:
Graphene layer is deposited on the surface of nano-patterned sapphire substrate;
Corona treatment is carried out to the graphene layer;And
The epitaxial growth aln layer on the graphene layer after processing.
In some embodiments, the corona treatment is carried out using nitrogen plasma.
In some embodiments, the power of the corona treatment is 10-200W.
In some embodiments, the flow of the corona treatment is 10-500sccm.
In some embodiments, the time of the corona treatment is 10s-60s.
In some embodiments, the pressure of the corona treatment is 100-1000Pa.
In some embodiments, the surface roughness of the aln layer is 0.2-1nm.
In some embodiments, the aln layer by Metallo-Organic Chemical Vapor deposition, hydride gas-phase epitaxy, splash Penetrate or molecular beam epitaxy and formed.
The present invention is using graphene nano graphical sapphire substrate as the substrate of aluminium nitride epitaxial growth, and to graphite Alkene layer carries out corona treatment, reduces lattice mismatch using the property of Van der Waals extension as buffer layer by means of graphene With high stress caused by thermal mismatching and high dislocation density, thus effectively promoted epitaxial nitride aluminium film quality.Present invention preparation Method is simple, and universality is high, is suitble to industrial mass manufacture.
Detailed description of the invention
Figure 1A is the scanning electron microscopy of the aluminium nitride film of epitaxial growth on Conventional nano graphical sapphire substrate Mirror figure;
Figure 1B is that the scanning electron of the aluminium nitride film of epitaxial growth on graphene nano graphical sapphire substrate is aobvious Micro mirror figure;
Fig. 2 is the atomic force microscope of the aluminium nitride film of epitaxial growth on graphene nano graphical sapphire substrate Figure;
Fig. 3 A is that the X-ray diffraction of the aluminium nitride film of epitaxial growth on Conventional nano graphical sapphire substrate waves Curve;
Fig. 3 B is that the X-ray diffraction of the aluminium nitride film of epitaxial growth on graphene nano graphical sapphire substrate shakes Put curve;
Fig. 4 is the epitaxial growth on Conventional nano graphical sapphire substrate and graphene nano graphical sapphire substrate Aluminium nitride film Raman test chart.
Specific embodiment
Below according to specific embodiment, technical scheme is described further.Protection scope of the present invention is unlimited In following embodiment, these examples are enumerated merely for exemplary purpose without limiting the invention in any way.
The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate of the invention, is in nano graph first The surface for changing Sapphire Substrate deposits graphene layer, obtains graphene nano graphical sapphire substrate.
The method for depositing graphene layer can be chemical vapour deposition technique, step can include: by nano patterning sapphire Substrate is placed in reaction cavity, and reaction temperature (such as 1000-1200 DEG C) is warming up under oxygen atmosphere, and annealing is pre- under this condition 4h is handled, oxygen is closed later, is drained oxygen in system using inert gas, hydrogen is passed through and carbon source carries out the change of graphene Vapor deposition reaction is learned, so that graphene layer is deposited on nano-patterned sapphire substrate.
Nano-patterned sapphire substrate has specific nano graph, such as cone cell, platform-like, pothole shape etc..Graphite Alkene layer may include one or more layers graphene, such as 1-3 layers of graphene.
It needs to carry out corona treatment to graphene layer after deposition graphene layer, so that the aln layer of itself and subsequent growth Form good matching effect.
Corona treatment can be nitrogen plasma treatment, and wherein nitrogen flow is 10-500sccm, power 10- 200w, time 10-60s, pressure 100-1000Pa.
It is plasma treated, the epitaxial growth aln layer on graphene layer, the rough surface of gained aln layer Degree is 0.2-1nm, it is sufficient to meet the level requirements of subsequent technique.The method of growing aluminum nitride layer can be Metallo-Organic Chemical Vapor Deposition, hydride gas-phase epitaxy, sputtering or molecular beam epitaxy etc..
The present invention is described in further detail by the following examples.
Embodiment
Unless otherwise specified, experimental method used in following embodiments is conventional method.
Unless otherwise specified, the materials, reagents and the like used in the following examples is commercially available.
The epitaxial growth aluminium nitride film on graphene nano graphical sapphire substrate of embodiment 1.
1) graphene layer is deposited on the surface of nano-patterned sapphire substrate.
Nano-patterned sapphire substrate is placed in reaction cavity, 1100 DEG C are warming up under 300sccm oxygen atmosphere, And annealing pre-processes 4h under this condition, closes oxygen later, is drained oxygen in system using argon gas, holding flow is 500sccm is passed through 200sccm hydrogen and 15sccm methane, carries out the chemical vapour deposition reaction of graphene, reaction time 8h, To which graphene layer is deposited on nano-patterned sapphire substrate.
2) nitrogen plasma treatment is carried out to graphene nano graphical sapphire substrate.
Graphene nano graphical sapphire substrate is put into plasma process chamber, adjusting nitrogen flow is 15sccm, power 90w, pressure 500Pa carry out 30s corona treatment.
3) the epitaxial growth aluminium nitride film on plasma treated graphene nano graphical sapphire substrate.
Plasma treated graphene graphical sapphire substrate is put into mocvd growth chamber, heating substrate is extremely 1200 DEG C, adjust TMAl flow 50sccm, NH3Flow 500sccm, growth chamber pressure are 50torr, use N2It is raw as carrier gas Long 1h obtains the AlN film of high quality.
With scanning electron microscope, measure respectively graphical in Conventional nano graphical sapphire substrate and graphene nano The surface topography of the aluminium nitride film of Grown on Sapphire Substrates, as a result as shown in FIG. 1A and 1B, wherein Figure 1A be The scanning electron microscope diagram of the aluminium nitride film of epitaxial growth on Conventional nano graphical sapphire substrate;Figure 1B is in graphite The scanning electron microscope diagram of the aluminium nitride film of epitaxial growth on alkene nano-patterned sapphire substrate.It can from Figure 1A Out, growing aluminum nitride film is discontinuous island structure on Conventional nano graphical sapphire substrate, irregular;And from Figure 1B can be seen that the aluminum nitride thin film surface continuous formation grown on graphene nano graphical sapphire substrate.
For further verify growth aluminium nitride film profile pattern, use atomic force microscope measure aluminum nitride thin The surface roughness of film, as a result as shown in Figure 2.From figure 2 it can be seen that raw on graphene nano graphical sapphire substrate The surface roughness of long aluminium nitride film is 0.3nm, is atomically flating.
Using the rocking curve of X-ray diffraction test aluminium nitride film, the dislocation in film can be assessed by halfwidth As a result density is schemed as shown in Figure 3A and Figure 3B, wherein Fig. 3 A is the epitaxial growth on Conventional nano graphical sapphire substrate The X-ray diffraction rocking curve of aluminium nitride film;Fig. 3 B is the epitaxial growth on graphene nano graphical sapphire substrate The X-ray diffraction rocking curve of aluminium nitride film.As can be seen from Figure 3A, the nitrogen grown in graphene nano patterned substrate Changing aluminium film (0002) peak has smaller halfwidth.As can be seen from Figure 3B, it is grown in graphene nano patterned substrate The aluminium nitride film peak (10-12) have smaller halfwidth.It is converted to dislocation density, threading dislocation density 2.70E+08, sword Dislocation density 6.82E+09 reduces an at least number compared to the Conventional nano patterned substrate dislocation density in not graphene Magnitude.
Using Raman spectrum test in the Raman shift of aluminium nitride film, answering in film can be assessed by Raman peak position Power size, as a result as shown in Figure 4.It can be seen from the figure that with the epitaxial growth on Conventional nano graphical sapphire substrate Aluminium nitride film is compared, the aluminium nitride film Raman peak position grown in graphene nano patterned substrate more towards with intrinsic body Peak position, Raman shift is from 662.5cm-1Become 658.8cm-1, stress intensity is reduced into 0.378GPa from 1.378Ga, significantly reduces Stress.
In conclusion the present invention is using graphene nano graphical sapphire substrate as the lining of aluminium nitride epitaxial growth Bottom, and corona treatment is carried out to graphene layer, by means of graphene as buffer layer, using the property of Van der Waals extension, High stress and high dislocation density caused by lattice mismatch and thermal mismatching are reduced, to effectively promote the matter of epitaxial nitride aluminium film Amount.Preparation method of the present invention is simple, and universality is high, is suitble to industrial mass manufacture.
Those skilled in the art should be noted that embodiment described in the invention is only exemplary, can be Various other replacements, changes and improvements are made in the scope of the present invention.Thus, the present invention is not limited to the above embodiments, and only It is defined by the claims.

Claims (8)

1. a kind of method of the epitaxial growth aluminium nitride on nano-patterned sapphire substrate, comprising:
Graphene layer is deposited on the surface of nano-patterned sapphire substrate;
Corona treatment is carried out to the graphene layer;And
The epitaxial growth aln layer on the graphene layer after processing.
2. according to the method described in claim 1, wherein the corona treatment is carried out using nitrogen plasma.
3. according to the method described in claim 2, wherein the power of the corona treatment is 10-200W.
4. according to the method described in claim 2, wherein the flow of the corona treatment is 10-500sccm.
5. according to the method described in claim 2, wherein the time of the corona treatment is 10-60s.
6. according to the method described in claim 2, wherein the pressure of the corona treatment is 100-1000Pa.
7. according to the method described in claim 1, wherein the surface roughness of the aln layer is 0.2-1nm.
8. method according to any one of claim 1 to 7, wherein the aln layer passes through Metallo-Organic Chemical Vapor Deposition, hydride gas-phase epitaxy, sputtering or molecular beam epitaxy and formed.
CN201810973406.6A 2018-08-24 2018-08-24 The method of epitaxial growth aluminium nitride on nano-patterned sapphire substrate Pending CN109119327A (en)

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PCT/CN2019/092806 WO2020038103A1 (en) 2018-08-24 2019-06-25 Nano patterned sapphire substrate with graphene, preparation method therefor and use thereof, graphene ultraviolet led and preparation method therefor

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020038103A1 (en) * 2018-08-24 2020-02-27 北京石墨烯研究院 Nano patterned sapphire substrate with graphene, preparation method therefor and use thereof, graphene ultraviolet led and preparation method therefor
CN112086343A (en) * 2020-08-24 2020-12-15 中国科学院长春光学精密机械与物理研究所 Hexagonal boron nitride film growth method and hexagonal boron nitride film
CN114284397A (en) * 2020-09-27 2022-04-05 中国科学院半导体研究所 Method for growing high-quality aluminum nitride film on foreign substrate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110129675A1 (en) * 2009-12-01 2011-06-02 Samsung Electronics Co., Ltd. Material including graphene and an inorganic material and method of manufacturing the material
CN106868472A (en) * 2017-01-19 2017-06-20 中国工程物理研究院电子工程研究所 The growing method and gallium nitride lasers of a kind of nitride epitaxial piece
CN108010995A (en) * 2017-12-01 2018-05-08 北京大学 A kind of high light efficiency LED chip based on graphene Sapphire Substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110129675A1 (en) * 2009-12-01 2011-06-02 Samsung Electronics Co., Ltd. Material including graphene and an inorganic material and method of manufacturing the material
CN106868472A (en) * 2017-01-19 2017-06-20 中国工程物理研究院电子工程研究所 The growing method and gallium nitride lasers of a kind of nitride epitaxial piece
CN108010995A (en) * 2017-12-01 2018-05-08 北京大学 A kind of high light efficiency LED chip based on graphene Sapphire Substrate

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020038103A1 (en) * 2018-08-24 2020-02-27 北京石墨烯研究院 Nano patterned sapphire substrate with graphene, preparation method therefor and use thereof, graphene ultraviolet led and preparation method therefor
CN112086343A (en) * 2020-08-24 2020-12-15 中国科学院长春光学精密机械与物理研究所 Hexagonal boron nitride film growth method and hexagonal boron nitride film
CN114284397A (en) * 2020-09-27 2022-04-05 中国科学院半导体研究所 Method for growing high-quality aluminum nitride film on foreign substrate

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Application publication date: 20190101