CN102201503A - III-nitride substrate growing method, substrate and LED (light emitting diode) - Google Patents
III-nitride substrate growing method, substrate and LED (light emitting diode) Download PDFInfo
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- CN102201503A CN102201503A CN2011100781318A CN201110078131A CN102201503A CN 102201503 A CN102201503 A CN 102201503A CN 2011100781318 A CN2011100781318 A CN 2011100781318A CN 201110078131 A CN201110078131 A CN 201110078131A CN 102201503 A CN102201503 A CN 102201503A
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Abstract
A III-nitride substrate growing method comprises the following steps: providing a copper support substrate; forming a graphene layer on the surface of the support substrate; and forming a III-nitride semiconductor layer on the surface of the graphene layer, wherein the highest growing temperature of the III-nitride semiconductor layer is lower than the melting point of copper. In the method, since graphene and III-nitride are sequentially grown on the conductive metallic copper substrate with high melting point, growth process is simple and impurities cannot be introduced in the production process.
Description
Technical field
The present invention relates to semiconductor device and technology field, relate in particular to a kind of growing method and substrate of III group-III nitride substrate.
Background technology
III group-III nitride and ternary alloy three-partalloys thereof such as gallium nitride and indium nitride, aluminium nitride as third generation semi-conducting material, are the research focuses of field of semiconductor materials in recent years, also have been widely used in a plurality of fields in the productive life simultaneously.III group-III nitride and alloy thereof all are direct gap semiconductors, and particularly the ratio of passing through its component of adjustment of the alloy of three kinds of component compositions can be with the energy gap successive control in the scope from 1.9eV to 6.2eV.In addition,, can form the two-dimensional electron gas of high concentration, high mobility, remedy the defective that the wide bandgap semiconductor electron effective mass is big, mobility is low by the heterojunction structure that III group-III nitride and alloy thereof are made.At present, the main application fields of III group-III nitride comprises indigo plant, green light LED, laser diode, high frequency, high-temperature electronic device, solar cell etc.Along with the maturation of resilient coating technology and III group-III nitride p type doping techniques, the research of III group nitride material has obtained interim achievement.Realized industrialization at present as high brightness indigo plant, green light LEDs such as InGaN.And the famous manufacturers such as Cree company of the Ri Ya company (Nichia) of Japan and the U.S. also are being engaged in the production and the research of gallium nitride based light emitting diode for many years always.
Graphene can utilize chemical vapour deposition (CVD) as a kind of very novel material, and methods such as graphite oxidation reduction and mechanical cleavage make, and are a kind of zero band gap, semimetallic two-dimensional material.Carrier moving speed in the Graphene can reach 1/300 of the light velocity, and its electron mobility experiment measuring value surpasses 15000cm
2/ vs (carrier concentration n ≈ 10
13Cm
-2), in 10~100K scope, mobility is almost temperature independent.The lattice constant of Graphene is 0.246nm, and the lattice constant of gallium nitride C face is 0.319nm, and the ratio of the two was near 3: 4, and the lattice mismatch on this ratio is no more than 3%.In addition, Graphene has lower charge carrier injection barrier, the material softness, and thermodynamic stability is strong, is considered to a kind of critical material that is applied to electronics and optoelectronics field becoming in the future.
The good photoelectric characteristic of the electrology characteristic of above-mentioned Graphene excellence and III group-III nitride combines, and helps improving traditional performance of semiconductor device based on nitride.Had report in the document in this regard, and for example be published in 2010 just to mention among the document Large-scalepatterned multilayer grapheme films as transparent conducting electrodes for GaNlight-emitting diodes of 175201 pages of the 21st phases of Nanotechnology in gallium nitride light-emitting diode and replace of the application of ITO electro-conductive glass as transparency electrode with Graphene.But the method more complicated of transferring to III group-III nitride surface (as spin coating poly dimethyl silane, steps such as poly dimethyl silane are dissolved in chemical corrosion again) of Graphene in these reports, and cause the fold of Graphene easily and introduce impurity.
Summary of the invention
Technical problem to be solved by this invention is, a kind of growing method and substrate thereof of III group-III nitride substrate is provided, and the III group-III nitride is grown directly upon the Graphene surface, helps to overcome the growth technique complexity, and Graphene fold and introduce problems such as impurity.
In order to address the above problem, the invention provides a kind of growing method of III group-III nitride substrate, comprise the steps: to provide support substrate, the surface of described support substrates is an III nitride semiconductor layer; III nitride semiconductor layer surface in support substrates forms graphene layer; Form the 2nd III nitride semiconductor layer on the graphene layer surface.
As optional technical scheme, the preparation method of described graphene layer is selected from a kind of in the method for chemical vapour deposition (CVD) or the graphite oxidation method of reducing.
As optional technical scheme, the thickness of described graphene layer is 1~100 atomic layer.
As optional technical scheme, adopt MOCVD prepared the 2nd III nitride semiconductor layer.
As optional technical scheme, the material of described first and second III nitride semiconductor layer is selected from a kind of or combination in gallium nitride, aluminium nitride, the indium nitride independently of one another.
The present invention further provides a kind of III group-III nitride substrate, comprised support substrates, the surface of described support substrates is an III nitride semiconductor layer; The graphene layer on the one III nitride semiconductor layer surface of support substrates; And the 2nd III nitride semiconductor layer on graphene layer surface.
As optional technical scheme, the thickness of described graphene layer is 1~100 atomic layer.
As optional technical scheme, the material of described first and second III nitride semiconductor layer is selected from a kind of or combination in gallium nitride, aluminium nitride, the indium nitride independently of one another.
A kind of III group-III nitride LED comprises: support substrates, the surface of described support substrates are an III nitride semiconductor layer; The graphene layer on the one III nitride semiconductor layer surface of support substrates; The 2nd III nitride semiconductor layer on graphene layer surface, described the 2nd III group iii nitride layer further comprises first conductive type semiconductor layer, second conductive type semiconductor layer and is clipped between the two active layer that wherein first conductive type semiconductor layer contacts with Graphene; First electrode and second electrode, wherein first electrode contacts with Graphene, and second electrode contacts with second conductive type semiconductor layer.
The invention has the advantages that, adopt III group-III nitride substrate as growth substrates, grow successively again Graphene and III group-III nitride, growth technique is simple, and can not introduce impurity in process of production.
Description of drawings
It shown in the accompanying drawing 1 structural representation that adopts the III group-III nitride substrate of the described method growth of the specific embodiment of the invention.
The structure that is shown in the accompanying drawing 2 with accompanying drawing 1 is the LED structural representation that the basis forms.
Embodiment
Below in conjunction with accompanying drawing the growing method of a kind of III group-III nitride substrate provided by the invention and the embodiment of substrate are elaborated.
Below be that example describes to adopt MOCVD technology growing GaN, except on the concrete parameter of growth technique slightly the difference, all the other are all roughly the same with following execution mode for materials such as AlN, InN and InGaN.
The preparation of Graphene: can select the method or the preparation of graphite oxidation method of reducing of chemical vapour deposition (CVD) for use, preferred chemical gaseous phase depositing process.Embodiment about chemical vapour deposition technique belongs to known technology, no longer is described in detail herein.
The transfer of Graphene: spin coating dimethyl silicone polymer (PDMS) layer on graphene film, because PDMS has certain viscosity, can adhere to the graphene film layer, and utilize chemical method corrosion Graphene substrate, thereby the graphene film layer is peeled off from growth substrates.
The laminated film lamination of graphene film and PDMS layer formation is imprinted on intrinsic GaN plane of crystal.In this step, graphene film and intrinsic GaN crystal fit tightly.The intrinsic GaN crystal here can be the self-supporting substrate that adopts technology growth such as HPVE, or the crystal film that adopts technology such as MOCVD to grow on support substrates such as sapphire.
With the lip-deep Graphene of the above-mentioned GaN of transferring to is buffer growth GaN, and concrete steps are as follows:
Substrate heating: the reaction vessel that the intrinsic GaN crystal supporter that will be coated with Graphene is put into an anaerobic and do not had hydrogen is heated to 800~1000 ℃.
Growing gallium nitride: under above-mentioned underlayer temperature, feeding flow in reaction vessel is the trimethyl gallium of 150~200 μ mol/min and the ammonia of 9~12slpm, grows 1~10 hour.This step also can be selected MBE or HVPE for use, but the minimum temperature in the growth course should be higher than the fusing point on GaN support substrates surface.
Be the III group-III nitride substrate that adopts the said method growth shown in the accompanying drawing 1, comprise GaN layer 1, graphene layer 2 and GaN support substrates 3.Certainly, also can select for use other material to replace GaN support substrates 3, AlN, InP or their threes' alloy for example, the GaN layer on surface also can replace AlN, InP or their threes' alloy.Which kind of which kind of as support substrates and at Graphene superficial growth crystal, can freely select by those skilled in the art with material.
Said structure can be as making the LED structure.The LED ray structure of continued growth band active layer on above-mentioned III group-III nitride substrate, and employing conventional method etching electrode, promptly form the LED structure of the structure of the accompanying drawing 1 shown in the accompanying drawing 2 for basis formation, comprise: support substrates 20, the surface of described support substrates 20 are an III nitride semiconductor layer 21; The graphene layer 23 on the one III nitride semiconductor layer 21 surfaces; The 2nd III nitride semiconductor layer 22 on graphene layer 23 surfaces, described the 2nd III group iii nitride layer 22 further comprises first conductive type semiconductor layer 221, second conductive type semiconductor layer 222 and is clipped between the two active layer 223 that wherein first conductive type semiconductor layer 221 contacts with graphene layer 23; First electrode 241 and second electrode 242, wherein first electrode 241 contacts with graphene layer 23, and second electrode 242 contacts with second conductive type semiconductor layer 222.
Adopt the advantage of the LED of said structure to be, the path of LED operating current will be to carry out along the path of " the first electrode 241-graphene layer 23-the 2nd III nitride semiconductor layer 22-, second electrode 242 ", the conductivity of graphene layer 23 is very high, with metal species seemingly, so structure has realized the perpendicular flow of electric current in LED inside, reduced the series resistance of LED, effect is equivalent to the LED of vertical stratification.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. the growing method of an III group-III nitride substrate is characterized in that, comprises the steps: to provide support substrate, and the surface of described support substrates is an III nitride semiconductor layer; III nitride semiconductor layer surface in support substrates forms graphene layer; Form the 2nd III nitride semiconductor layer on the graphene layer surface.
2. growing method according to claim 1 is characterized in that, the preparation method of described graphene layer is selected from a kind of in the method for chemical vapour deposition (CVD) or the graphite oxidation method of reducing.
3. growing method according to claim 1 is characterized in that, the thickness of described graphene layer is 1~100 atomic layer.
4. growing method according to claim 1 is characterized in that, adopts MOCVD prepared the 2nd III nitride semiconductor layer.
5. growing method according to claim 1 is characterized in that, the material of described first and second III nitride semiconductor layer is selected from a kind of or combination in gallium nitride, aluminium nitride, the indium nitride independently of one another.
6. an III group-III nitride substrate is characterized in that, comprises support substrates, and the surface of described support substrates is an III nitride semiconductor layer; The graphene layer on the one III nitride semiconductor layer surface of support substrates; And the 2nd III nitride semiconductor layer on graphene layer surface.
7. III group-III nitride substrate according to claim 6 is characterized in that, the thickness of described graphene layer is 1~100 atomic layer.
8. III group-III nitride substrate according to claim 6 is characterized in that, the material of described first and second III nitride semiconductor layer is selected from a kind of or combination in gallium nitride, aluminium nitride, the indium nitride independently of one another.
9. an III group-III nitride LED is characterized in that, comprising:
Support substrates, the surface of described support substrates are an III nitride semiconductor layer;
The graphene layer on the one III nitride semiconductor layer surface;
The 2nd III nitride semiconductor layer on graphene layer surface, described the 2nd III group iii nitride layer further comprises first conductive type semiconductor layer, second conductive type semiconductor layer and is clipped between the two active layer that wherein first conductive type semiconductor layer contacts with graphene layer; First electrode and second electrode, wherein first electrode contacts with graphene layer, and second electrode contacts with second conductive type semiconductor layer.
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CN102412352A (en) * | 2011-11-10 | 2012-04-11 | 杭州创元光电科技有限公司 | High-power LED (light-emitting diode) light source packaging structure manufactured by graphene and production process thereof |
CN103378239A (en) * | 2012-04-25 | 2013-10-30 | 清华大学 | Epitaxial structure body |
CN103374751A (en) * | 2012-04-25 | 2013-10-30 | 清华大学 | Preparation method of extensional structural body with micro-structure |
CN103794469A (en) * | 2012-10-30 | 2014-05-14 | 北京北方微电子基地设备工艺研究中心有限责任公司 | Preparation method of gallium nitride film layer and substrate |
CN104009130A (en) * | 2013-02-22 | 2014-08-27 | Lg电子株式会社 | Growth substrate, nitride semiconductor device and method of manufacturing the same |
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US9083004B2 (en) | 2013-07-18 | 2015-07-14 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Light-emitting device and manufacturing method thereof |
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US9190565B2 (en) | 2012-04-25 | 2015-11-17 | Tsinghua University | Light emitting diode |
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US9666759B2 (en) | 2013-02-22 | 2017-05-30 | Lg Electronics Inc. | Growth substrate, nitride semiconductor device and method of manufacturing the same |
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Application publication date: 20110928 |