CN102769081A - Structure using graphite alkene as buffer layer epitaxy GaN (gallium nitride) and preparation method of structure - Google Patents
Structure using graphite alkene as buffer layer epitaxy GaN (gallium nitride) and preparation method of structure Download PDFInfo
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Abstract
The invention relates to a structure using graphite alkene as buffer layer epitaxy GaN (gallium nitride) and a preparation method of the structure. The method comprises the following steps of: adopting a graphite alkene layer as a buffer layer between the substrate and a gallium nitride epitaxy layer; and inserting a nitride thin layer between the graphite alkene layer and a GaN layer so as to obtain a gallium nitride epitaxy layer with low stress and high quality. The defective rate of LED (light emitting diode) devices is reduced, the quality of the LED devices is increased, and the life cycle is prolonged. The problem of lattice mismatch and thermal expansion coefficient mismatch between the substrate and the gallium nitride are solved effectively.
Description
Technical field
The present invention relates to a kind of with Graphene as structure of resilient coating extension GaN and preparation method thereof, belong to the photoelectron technology field.
Background technology
Gallium nitride material has been received increasing concern as a kind of novel semi-conducting material.As the semi-conductive representative materials of the third generation, gallium nitride has excellent electricity and optical property, and it has the advantage than broad-band gap, direct band gap, and high temperature high voltage resistant is fit to be applied in the environment of inclement condition.The main application of gallium nitride material is light-emitting diode (LED) and HEMT.Gallium nitride based light emitting diode can be realized the wavelength variations from the ultraviolet to ruddiness, has covered whole visible light wave range, and the especially commercialization of gallium nitride blue LED has driven the development of field of semiconductor illumination.At present, light-emitting diode is widely used in traffic lights, panchromatic demonstration, LCD screen backlight, automobile instrument and built-in light etc.In the last few years, UV LED came into the market, and was mainly used in the detection (like the detection of absorption region at the bacterial spore of 260-340nm) of biomone, purifying, medical treatment and the diagnosis etc. of empty G&W.Compare with general light-emitting diode, UV LED is higher to the quality requirement of material.
Because obtaining of gallium nitride material monocrystalline is very difficult, cost is also very high, and therefore gallium nitride material generally is grown in (sapphire, carborundum, silicon etc.) on the foreign substrate at present.Need solve the nuclear issue that becomes between substrate and the epitaxial loayer in growth material on the foreign substrate, owing to there is the difference of lattice constant and wetability between the material, heteroepitaxy need realize through resilient coating.Resilient coating can play the effect of alleviating lattice mismatch between substrate and the epitaxial loayer, can play wetting effect simultaneously, effectively improves the crystal mass of epitaxial material.But the existence of resilient coating can only be alleviated a part of lattice mismatch, and the gallium nitride epitaxial materials of actual growth still has the dislocation of higher density.
All once mentioned in China and foreign countries' patent documentation and adopted the problem that solves lattice mismatch with the approaching relatively material of character of extension gallium nitride layer: Japan Patent JP7312350 " CRYSTAL GROWTH METHOD OF GALLIUM NITRIDE-BASED COMPOUND SEMICONDUCTOR "; This patent discloses a kind of method of on Sapphire Substrate, utilizing aluminum gallium nitride resilient coating extension gallium nitride; This resilient coating adopts the growth of metal-organic chemical vapor deposition equipment method, can obtain the high-quality gallium nitride material of minute surface; U.S. Pat 6495867 " InGaN/AlGaN/GaN Mutilayer Buffer For Growth Of GaN On Sapphire " discloses a kind of structure of compound buffer layer, and it adopts the compound buffer layer of indium gallium nitrogen, aluminum gallium nitride, gallium nitride to reduce the mismatch degree between sapphire and the gallium nitride; Chinese patent CN1505843 " the GaN base LED that on the SiC substrate, forms "; It is the structure and the preparation method of master's complicated resilient coating with the AlGaN material on the SiC substrate that this patent discloses a kind of, the problem of the material wetability difference when this method has solved extension gallium nitride on the silicon carbide substrates.Though the above-mentioned technological means that several patents adopted can be alleviated lattice mismatch, but can not relax stress and coefficient of thermal expansion mismatch between substrate and the epitaxial material.Therefore, when epitaxial growth, can cause the epitaxial crystal quality to decrease owing to the bigger stress of existence, even crackle occur.
CN101385126A proposes a kind of device that comprises the graphene layer of epitaxial growth on single crystalline substrate, and specifically be logged into: like fabricate devices on Graphene, the lattice mismatch of this device and Graphene must be very little so, and promptly lattice mismatch is less than about 2%.In embodiment, providing the said material that has with the basic lattice match of Graphene is multilayer hexagon BN.The application quotes the full text of this patent documentation as prior art.
Summary of the invention
The present invention is directed to the deficiency that has epitaxial growth GaN on resilient coating now, proposed a kind of on the SiC substrate with the structure of Graphene as resilient coating extension GaN.
The present invention also propose a kind of on the SiC substrate with the preparation method of Graphene as the structure of resilient coating extension GaN, not only reduced the stress of epitaxial material, and improved the epitaxial crystal quality.
The present invention also proposes a kind of GaN base LED of graphitiferous alkene resilient coating.
Technical scheme of the present invention is following:
A kind of with the structure of Graphene as resilient coating extension GaN; Comprise resilient coating and GaN layer; Described resilient coating is a graphene layer; Graphene layer is grown on the silicon carbide substrates, between graphene layer and GaN layer, is inserted with nitride thin layer, and the structure of said extension GaN is substrate, graphene layer, nitride thin layer and GaN layer from bottom to top successively.
According to the present invention, the number of plies 1-50 layer of said graphene layer; Preferably, the number of plies of graphene layer is the 1-30 layer.
According to the present invention, the thickness of said GaN layer is 2 μ m-8 μ m; Preferably, the thickness of GaN layer is 6 μ m-8 μ m.
According to the present invention, said nitride thin layer thickness is 10-300nm, further preferably as follows:
Said nitride thin layer is the aluminum gallium nitride thin layer, and thickness is 10-200nm; Preferably, the aluminum gallium nitride thickness of thin layer is 100nm.
Said nitride thin layer is an indium gallium nitrogen thin layer, and thickness is 20-300nm; Preferably, indium gallium nitrogen thickness of thin layer is 150nm.
According to the present invention, the thickness of described substrate layer is 200-1000 μ m; Preferably, the thickness of substrate layer is 500-700 μ m.
The structure of extension GaN of the present invention has not only reduced the stress of GaN epitaxial loayer with Graphene as supple buffer layer, and has improved the quality of epitaxial crystal.Adopt the transition of aluminum gallium nitride or indium gallium nitrogen thin layer, reduced the difficulty that differs the GaN layer epitaxially grown that (about 20%) greatly bring because of the lattice mismatch of GaN layer and graphene layer.
A kind ofly comprise with the method for Graphene as resilient coating epitaxial growth GaN on silicon carbide substrates,
1) on the silicon carbide substrates layer, prepares graphene layer;
2) growth one deck nitride thin layer on graphene layer;
3) on nitride thin layer, adopt metal-organic chemical vapor deposition equipment method growing GaN layer, growth rate is 0.5 μ m/h～6 μ m/h, and growth temperature is 900-1200 ℃, and thickness is 2 μ m-8 μ m, and the carrier gas of using is nitrogen and hydrogen mixed gas.
The thickness of above-mentioned GaN layer is 2 μ m-8 μ m; The thickness of preferred GaN layer is 6 μ m-8 μ m;
Above-mentioned nitride thin layer is aluminum gallium nitride thin layer or indium gallium nitrogen thin layer; Wherein, said aluminum gallium nitride thickness of thin layer is 10nm-200nm, and preferred aluminum gallium nitride thickness of thin layer is about 100nm, and growth temperature is 500 ℃-1000 ℃, and the growth rate scope is 1nm/min-100nm/min, and the carrier gas of using is nitrogen and hydrogen mixed gas; The thickness of said indium gallium nitrogen thin layer is 20-300nm, and preferred indium gallium nitrogen thickness of thin layer is about 150nm, and growth temperature is 300 ℃-700 ℃, and the growth rate scope is 0.1nm/min-60nm/min; The carrier gas of using is nitrogen and hydrogen mixed gas.
In the above method in the used carrier gas volume ratio of nitrogen and hydrogen mixed gas be (1～5): (5～1) comprise the growth of nitride thin layer and GaN layer.
Above-mentioned steps 1) method that on substrate layer, prepares graphene layer in is a physical vaporous deposition, and this method is that substrate layer is put in the dielectric heating oven of high vacuum, temperature is heated to 1400-1800 ℃ carries out the Graphene growth.Said method is quoted as a reference as known technology.
A kind of GaN of graphitiferous alkene resilient coating base LED comprises the structure of extension GaN of the present invention comprising from bottom to top silicon carbide substrates, graphene layer, nitride thin layer and GaN layer.The preparation of the GaN base LED of said graphitiferous alkene resilient coating is included in and continues epitaxial growth N type GaN, InGaN/GaN MQW active area, P type AlGaN and P type GaN on the above-mentioned GaN layer, prepares P, N electrode afterwards respectively, finally makes GaN base LED.
Compared with prior art, excellent results of the present invention is:
1) the present invention passes through to adopt graphene layer as the resilient coating between silicon carbide substrates and the GaN epitaxial loayer, to obtain low stress, high quality GaN epitaxial loayer, reduces the defect rate of LED device, improves quality, the prolongation life cycle of LED device.
2) Grown GaN epitaxial loayer of the present invention has more low-density dislocation, thereby improves the mobility that perhaps improves the HEMT that on its basis, prepares in the brightness of the light-emitting diode for preparing on its basis, reduces the leakage current of device.
3) preparation method of the present invention has been alleviated lattice mismatch and the problem of coefficient of thermal expansion mismatch between substrate layer and the GaN layer effectively.
4) the present invention differs at the lattice mismatch of GaN layer and graphene layer under about 20% the situation, through the transition of aluminum gallium nitride or indium gallium nitrogen thin layer, reduces the difficulty of GaN layer epitaxially grown.
Description of drawings
Fig. 1 is the structural representation of extension GaN of the present invention; Wherein, 1, silicon carbide substrates layer; 2, graphene layer; 3, aluminum gallium nitride or indium gallium nitrogen thin layer (nitride thin layer); 4, GaN layer.
Fig. 2 is the normalization surface of intensity distribution when X-ray (002) half-peak breadth was reduced to 160 seconds by 240 seconds respectively of structure of the extension GaN of the embodiment of the invention 1.
Embodiment
Below in conjunction with embodiment and Figure of description the present invention is carried out detailed explanation, but be not limited thereto.
Embodiment 1,
A kind of with the structure of Graphene as resilient coating extension GaN, comprise silicon carbide substrates 1, graphene layer 2 and GaN layer 4; Between graphene layer 2 and GaN layer 4, be provided with aluminum gallium nitride thin layer 3; Be graphene layer 2, aluminum gallium nitride thin layer 3 and GaN layer successively on silicon carbide substrates 1.The thickness of described silicon carbide substrates 1 is 600 μ m; The thickness of said graphene layer is 10nm, and the number of plies is 30 layers; The thickness of said GaN layer 4 is 6 μ m: the thickness of said aluminum gallium nitride thin layer 3 is 100nm.
Embodiment 2,
A kind of preparation method of embodiment 1 said structure, step is following:
1) silicon carbide substrates is cleaned; On substrate, adopt physical vaporous deposition to prepare graphene layer; Substrate is put in the dielectric heating oven of high vacuum; The thickness of silicon carbide substrates is 600 μ m, temperature is heated to 1500 ℃ carries out Graphene growth by prior art, and the thickness of graphene layer is 10nm;
2) growth one deck aluminum gallium nitride thin layer 3 on the formed graphene layer in step 1), said aluminum gallium nitride thin layer 3 thickness are 100nm, and growth temperature is 900 ℃, and the growth rate scope is 30nm/min, and the carrier gas of using is nitrogen and 1: 1 volume ratio gaseous mixture of hydrogen;
3) on aluminum gallium nitride thin layer 3, adopt metal-organic chemical vapor deposition equipment method growing GaN layer 4, growth rate is 2 μ m/h, and growth temperature is 1000 ℃, and thickness is 6 μ m, and the carrier gas of using is the gaseous mixture of nitrogen and 1: 1 volume ratio of hydrogen.
Use said method Grown GaN layer 4, through test, its X-ray (002) half-peak breadth was reduced to 160 seconds by 240 seconds, and crystal mass improves obviously.As shown in Figure 2.
Embodiment 3,
A kind of with the structure of Graphene as resilient coating extension GaN, comprise silicon carbide substrates 1, graphene layer 2 and GaN layer 4; Between graphene layer 2 and GaN layer 4, be provided with indium gallium nitrogen thin layer 3; Be graphene layer 2, indium gallium nitrogen thin layer 3 and GaN layer successively on silicon carbide substrates 1.The thickness of described silicon carbide substrates 1 is 500 μ m; The thickness of said graphene layer is 10nm; The thickness of said GaN layer 4 is 8 μ m: the thickness of said indium gallium nitrogen thin layer 3 is 150nm.
Embodiment 4,
A kind of GaN base LED of graphitiferous alkene resilient coating comprises from bottom to top substrate, graphene layer, nitride thin layer and GaN layer.Of embodiment 1.
On above-mentioned GaN layer, continue epitaxial growth N type GaN, InGaN/GaN MQW active area, P type AlGaN and P type GaN, prepare P, N electrode afterwards respectively, make GaN base LED by prior art.
Claims (10)
1. one kind with the structure of Graphene as resilient coating extension GaN; Comprise resilient coating and GaN layer; Described resilient coating is a graphene layer; Graphene layer is grown on the silicon carbide substrates, between graphene layer and GaN layer, is inserted with nitride thin layer, and the structure of said extension GaN is substrate, graphene layer, nitride thin layer and GaN layer from bottom to top successively.
2. the structure of extension GaN as claimed in claim 1 is characterized in that, the number of plies 1-50 layer of said graphene layer; Preferably, the number of plies of graphene layer is the 1-30 layer.
3. the structure of extension GaN as claimed in claim 1 is characterized in that, the thickness of said GaN layer is 2 μ m-8 μ m; Preferably, the thickness of GaN layer is 6 μ m-8 μ m.
4. the structure of extension GaN as claimed in claim 1 is characterized in that, said nitride thin layer is the aluminum gallium nitride thin layer, and thickness is 10-200nm; Preferably, the aluminum gallium nitride thickness of thin layer is 100nm.
5. the structure of extension GaN as claimed in claim 1 is characterized in that, said nitride thin layer is an indium gallium nitrogen thin layer, and thickness is 20-300nm; Preferably, indium gallium nitrogen thickness of thin layer is 150nm.
6. the structure of extension GaN as claimed in claim 1 is characterized in that, the thickness of described substrate layer is 200-1000 μ m; Preferably, the thickness of substrate layer is 500-700 μ m.
7. the preparation method of the said structure of claim 1 is characterized in that, step is following:
1) on substrate, prepares graphene layer;
2) growth one deck nitride thin layer on graphene layer;
3) on nitride thin layer, adopt metal-organic chemical vapor deposition equipment method growing GaN layer, growth rate is 0.5 μ m/h～6 μ m/h, and growth temperature is 900-1200 ℃, and thickness is 2 μ m-8 μ m, and the carrier gas of using is nitrogen and hydrogen mixed gas.
8. preparation method as claimed in claim 7 is characterized in that, the thickness of said GaN layer is 2 μ m-8 μ m; Be preferably 6 μ m-8 μ m; Said nitride thin layer is aluminum gallium nitride thin layer or indium gallium nitrogen thin layer; Wherein,
Said aluminum gallium nitride thickness of thin layer is 10nm-200nm, and preferred aluminum gallium nitride thickness of thin layer is about 100nm, and growth temperature is 500 ℃-1000 ℃, and the growth rate scope is 1nm/min-100nm/min, and the carrier gas of using is nitrogen and hydrogen mixed gas;
The thickness of said indium gallium nitrogen thin layer is 20-300nm, and preferred indium gallium nitrogen thickness of thin layer is about 150nm, and growth temperature is 300 ℃-700 ℃, and the growth rate scope is 0.1nm/min-60nm/min; The carrier gas of using is nitrogen and hydrogen mixed gas.
9. preparation method as claimed in claim 7 is characterized in that, the volume ratio of nitrogen and hydrogen mixed gas is (1～5) in the said carrier gas: (5～1).
10. one kind contains the GaN base LED that right requires the structure of 1 said extension GaN; It is characterized in that; Be included in and continue epitaxial growth N type GaN, InGaN/GaN MQW active area, P type AlGaN and P type GaN on the above-mentioned GaN layer, prepare P, N electrode afterwards respectively, finally make GaN base LED.
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| CN111613697B (en) * | 2020-05-22 | 2020-11-27 | 山西穿越光电科技有限责任公司 | GaN/AlGaN superlattice thin film containing graphene intercalation and preparation method thereof |
| CN115810697A (en) * | 2023-02-10 | 2023-03-17 | 江西兆驰半导体有限公司 | Silicon-based ultraviolet LED epitaxial structure, preparation method thereof and ultraviolet LED |
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