CN207116374U - A kind of gallium nitride film and graphene film - Google Patents
A kind of gallium nitride film and graphene film Download PDFInfo
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- CN207116374U CN207116374U CN201720310168.1U CN201720310168U CN207116374U CN 207116374 U CN207116374 U CN 207116374U CN 201720310168 U CN201720310168 U CN 201720310168U CN 207116374 U CN207116374 U CN 207116374U
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Abstract
The utility model embodiment discloses a kind of gallium nitride film and graphene film, and the gallium nitride film includes：Semiconductor substrate, formed with nitride buffer layer in Semiconductor substrate；The graphene catalyst layer with the first pore structure and the graphene mask layer with the second pore structure are sequentially formed with nitride buffer layer, the first pore structure and the second pore structure are identical；The surface Epitaxial growth of exposed nitride buffer layer has gallium nitride layer on the surface of graphene mask layer and in the hole of graphene mask layer.In the utility model embodiment, mask epitaxial growth of gallium nitride layer is used as using the graphene mask layer with pore structure, the dislocation density of gallium nitride film growth on a semiconductor substrate can effectively be reduced, epitaxial layer of gallium nitride and the low angle grain boundary defect of graphene mask layer contact portion are effectively reduced, formed gallium nitride film is uniformly distributed and there is good crystal phase structure.
Description
Technical field
The utility model embodiment is related to thin film technique, more particularly to a kind of gallium nitride film and graphene film.
Background technology
Gallium nitride (GaN) has the advantages that energy gap is big, disruptive field intensity is high, electronic drifting rate is fast and bonded energy is high,
There are wide prospect and application in devices fields such as high temperature, high power, high pressure, high frequencies, therefore synthesis is with preparing gallium nitride
Manufacture the key of power electronic power device, microwave power device and photoelectric device.
The gallium nitride of C axles (0001) crystal face is the most widely used gallium nitride material in market so far, be can be applicable to each
In kind gallium-nitride-based devices, such as field-effect transistor (FETs) and the luminescent device (LEDs) of silicon substrate.Silicon (Si) substrate is in micro- electricity
Subdomains have extremely ripe development and application, and its monocrystalline quality is high, cost is low, size is big and can realize that photoelectricity integrates, because
This is highly suitable for the epitaxial film that group III-nitride is prepared on silicon, while can also meet to mass produce group III-nitride
Semi-conducting material and the demand of industrialization device application, synthesis at present and the substrate for preparing gallium nitride are (111) crystal orientation Si
Substrate.It is technically more ripe and can make however, the Si substrates of (100) crystal orientation compare (111) crystal orientation Si substrates
In most of electronic equipments, therefore the electronics of existing gallium-nitride-based devices and optoelectronic device commercialization receive serious limit
System.Obviously be vital in the Si Grown gallium nitride films of (100) crystal orientation, can make gallium nitride based electronic and
Optoelectronic device is commercialized.
But in the prior art, synthesized according to (100) crystal orientation Si substrates and prepare gallium nitride, because cube Si
(100) there is different symmetry in crystal face and six side GaN (0001) crystal faces, and high quality epitaxial growth gallium nitride film is in Si
(100) crystal face is extremely difficult.Even if using (111) crystal orientation Si substrate growth gallium nitride films generally used in the industry, two
The Macrolattice mismatch and coefficient of thermal expansion mismatch more than 17% are still suffered between kind material.Therefore it is directly brilliant in (100) or (111)
Body orientation Si Grown gallium nitride films are extremely difficult, and can cause higher lattice defect be present, have a strong impact on nitridation
Gallium film quality.
Graphene (Graphene) is a kind of honeycomb-like two-dimensional nano material of hexangle type being made up of sp2 hydbridized carbon atoms
Material, there is novel two-dimensional material characteristic, there is very high carrier mobility, high conduction performance and high-termal conductivity.At present, it is general
All over the industrialized production graphene film method used for transfer producing process, its transfer process complexity and vulnerable to pollution, it is not easy to big
Large-scale production, easily causes graphene film defect and stacks, and influences the overall integrity and stability of graphene film.
Utility model content
The utility model embodiment provides a kind of gallium nitride film and graphene film, to improve the film forming of gallium nitride film
Quality, and improve the stability of graphene film.
In a first aspect, the utility model embodiment provides a kind of gallium nitride film, the gallium nitride film includes：
Semiconductor substrate, formed with nitride buffer layer in the Semiconductor substrate；
Graphene catalyst layer with the first pore structure is sequentially formed with the nitride buffer layer and with second
The graphene mask layer of pore structure, first pore structure are identical with second pore structure；
The exposed gallium nitride on the surface of the graphene mask layer and in the hole of the graphene mask layer
The surface Epitaxial growth of cushion has gallium nitride layer.
Further, the Semiconductor substrate is silicon substrate, and the indices of crystallographic plane of the silicon substrate are (100) or (111).
Further, the thickness of the nitride buffer layer is less than or equal to 2 μm；
The thickness of the graphene catalyst layer is more than or equal to 0.2nm and is less than or equal to 10nm；
The thickness of the graphene mask layer is more than or equal to 0.2nm and is less than or equal to 2nm；
A side surface from the nitride buffer layer towards the Semiconductor substrate is to the gallium nitride layer away from described
The thickness of one side surface of Semiconductor substrate is more than or equal to 5 μm.
Further, the composition material of the graphene catalyst layer includes any one in Cu, Ni, Pt, Co, Ti and Fe
Kind, or, the composition material of the graphene catalyst layer includes the conjunction of any a variety of compositions in Cu, Ni, Pt, Co, Ti and Fe
Gold.
Second aspect, the utility model embodiment additionally provide a kind of graphene film, and the graphene film includes：
Semiconductor substrate；
On the semiconductor substrate formed with the graphene catalyst layer with the first pore structure；
Formed with the graphene layer with the second pore structure, first pore structure in the graphene catalyst layer
It is identical with second pore structure.
Further, the composition material of the graphene catalyst layer includes any one in Cu, Ni, Pt, Co, Ti and Fe
Kind, or, the composition material of the graphene catalyst layer includes the conjunction of any a variety of compositions in Cu, Ni, Pt, Co, Ti and Fe
Gold.
Further, the thickness of the graphene catalyst layer is more than or equal to 0.2nm and is less than or equal to 10nm；The stone
The thickness of black alkene layer is more than or equal to 0.2nm and is less than or equal to 2nm.
The gallium nitride film that the utility model embodiment provides, mask is used as using the graphene mask layer with pore structure
Epitaxial growth of gallium nitride layer；Fairly regular and flexible, hexagoinal lattice and the GaN tools of graphene are connected between the carbon atom of graphene
There is identical symmetry, GaN film can be according to graphene-structured autonomous growth, and the lattice between graphene and GaN material loses
With less than 3%, can effectively reducing the dislocation density of gallium nitride film growth on a semiconductor substrate, and single-layer graphene is two
Material is tieed up, can effectively reduce the low angle grain boundary defect of epitaxial layer of gallium nitride and graphene mask layer contact portion, at utmost
Reduce mask caused crystal defect, and the gallium nitride film formed can be uniformly distributed and have good crystalline phase in itself
Structure, the performance of gallium nitride film is thus improved, promote gallium nitride based electronic and optoelectronic device commercialization.The utility model is implemented
Example provide graphene film, on a semiconductor substrate growth in situ go out the graphene film with pore structure, the graphene
Film can be used as mask application, without using transfer producing process, without processing procedure is performed etching again after forming complete film layer, saving
Process；And preparation process is simple and will not introduce pollution, suitable for large-scale production, will not also cause graphene film to lack
Fall into and stack, improve the overall integrity and stability of graphene film.
Brief description of the drawings
, below will be to needed for embodiment description in order to illustrate more clearly of the technical scheme in the embodiment of the utility model
The accompanying drawing to be used does one and simply introduced, it should be apparent that, drawings in the following description are some implementations of the present utility model
Example, for those of ordinary skill in the art, on the premise of not paying creative work, can also be obtained according to these accompanying drawings
Obtain other accompanying drawings.
Fig. 1 is the flow chart of the preparation method for the gallium nitride film that the utility model embodiment one provides；
Fig. 2 is the schematic diagram for the gallium nitride film that the utility model embodiment one provides；
Fig. 3 A~Fig. 3 E are the schematic diagrames of the preparation technology for the gallium nitride film that the utility model embodiment two provides；
Fig. 4 is the schematic diagram for the graphene film that the utility model embodiment four provides；
Fig. 5 is the flow chart of the preparation method for the graphene film that the utility model embodiment four provides.
Embodiment
To make the purpose of this utility model, technical scheme and advantage clearer, implement hereinafter with reference to the utility model
Accompanying drawing in example, clearly and completely describes the technical solution of the utility model, it is clear that described implementation by embodiment
Example is the utility model part of the embodiment, rather than whole embodiments.Based on the embodiment in the utility model, this area
The every other embodiment that those of ordinary skill is obtained under the premise of creative work is not made, belongs to the utility model
The scope of protection.
As shown in figure 1, the flow chart of the preparation method of the gallium nitride film provided for the utility model embodiment one, with reference to
The structural representation for the gallium nitride film that Fig. 2 is provided, the technical scheme of the present embodiment is described in detail.The skill of the present embodiment
Art scheme is applied to the situation of the gallium nitride film of epitaxial growth high quality on a semiconductor substrate.
The preparation method for the gallium nitride film that the present embodiment provides, specifically comprises the following steps：
Step 110, semi-conductive substrate is provided, form nitride buffer layer on a semiconductor substrate.
Optional Semiconductor substrate is silicon substrate (Si), and the indices of crystallographic plane of silicon substrate are (100) or (111), and Silicon Wafer is micro-
Electronic applications have extremely ripe development and application, and its monocrystalline quality is high, cost is low, size is big and can realize that photoelectricity integrates,
Large-scale production GaN film is disclosure satisfy that as substrate and industrializes the demand of device application.Optional semiconductor in the present embodiment
Substrate is (100) high preferred orientation silicon substrate, and the technology of preparing of (100) high preferred orientation silicon substrate is ripe, has wide range of applications, can
Using in most of electronic equipments.Semiconductor substrate can be silicon carbide substrates or other crystal faces in other alternative embodiments
The silicon substrate of index, in the utility model Semiconductor substrate can be it is existing it is known any one can be used for preparing GaN it is thin
The Semiconductor substrate of film, such as sapphire etc., without concrete restriction in the utility model.
As shown in Fig. 2 gallium nitride (GaN) cushion 220 is formed in the present embodiment in Semiconductor substrate 210, GaN bufferings
Cushioning effect from layer 220 is used in follow-up GaN film forming, the buffering thicknesses of layers based on cushioning effect is generally than relatively thin, therefore
The thickness of GaN cushions 220 also can be than relatively thin in the present embodiment.Big lattice between Semiconductor substrate and GaN material generally be present
17% lattice mismatch and coefficient of thermal expansion mismatch between mismatch and coefficient of thermal expansion mismatch, such as Si substrates and GaN material be present,
And because the thickness ratio of GaN cushions 220 is relatively thin in the present embodiment, therefore between Semiconductor substrate 210 and GaN cushions 220
Macrolattice mismatch and coefficient of thermal expansion mismatch will not produce big lattice defect, dislocation density is relatively low, to GaN film forming
The influence of quality is relatively small.
Obviously, gallium nitride (GaN) cushion 220 is formed in Semiconductor substrate 210 not only to follow-up GaN quality of forming film
Influence smaller, additionally it is possible to play cushioning effect, be easy to the GaN film of epitaxial growth high quality.
Step 120, sequentially form on nitride buffer layer graphene catalyst layer with the first pore structure and with
The graphene mask layer of second pore structure, the first pore structure and the second pore structure are identical.
Graphene catalyst layer 230 and stone are formd as shown in Fig. 2 being stacked gradually in the present embodiment on GaN cushions 220
Black alkene mask layer 240, graphene catalyst layer 230 and graphene mask layer 240 have completely the same pore structure, therefore graphite
Each hole of alkene mask layer 240 can directly expose GaN cushions 220.Obvious graphene catalyst layer 230 not continuous film forming,
The film layer structure of optional graphene catalyst layer 230 is island film or chain film, and the pore structure of graphene catalyst layer 230 is nanometer
Level multi-pore structure, hole are uniformly distributed and are nano-scale dimension；Corresponding graphene mask layer 240 not continuous film forming, can
The film layer structure for selecting graphene mask layer 240 is island film or chain film, and the pore structure of graphene mask layer 240 is nanoscale
Multi-pore structure, hole are uniformly distributed and are nano-scale dimension.It will be understood by those skilled in the art that the film of graphene catalyst layer
Rotating fields include but is not limited to above example, and related practitioner can limit to form other different film layer knots according to technique and product
The graphene catalyst layer and graphene mask layer with hole of structure, without concrete restriction in the utility model.
The region of graphene catalyst layer 230 in the present embodiment on GaN cushions 220 only be present and can just grow graphene and cover
Film layer 240, the hole region of graphene catalyst layer 230 will not grow graphene mask layer 240.It is optional in the present embodiment
The composition material of graphene catalyst layer 230 includes any one in Cu, Ni, Pt, Co, Ti and Fe, or, graphene catalyst layer
230 composition material includes the alloy of any a variety of compositions in Cu, Ni, Pt, Co, Ti and Fe, i.e. graphene catalyst layer 230 is
Metal catalytic layer, above-mentioned metal or alloy are the conventional catalysis material of graphene.It will be understood by those skilled in the art that this practicality
The composition material of new middle graphene catalyst layer can be any one existing graphene catalysis material, be not limited to above-mentioned example.
Graphene mask layer 240 is grown in the region with graphene catalyst layer 230, graphene catalyst layer in the present embodiment
230 hole region will not grow graphene mask layer 240, therefore the graphene mask layer 240 formed has and graphite
Alkene Catalytic Layer 230 consistent film layer structure and pore structure.The as graphene film layer of graphene mask layer 240, graphene film layer
Composition material be carbon material.It will be understood by those skilled in the art that the technique of manufacture graphene film layer has a variety of, such as low pressure
Chemical vapour deposition technique (LPCVD), concrete restriction does not grow graphene mask in graphene catalyst layer in the utility model
The technique of layer.Compared with prior art, the present embodiment growth in situ graphene mask layer in graphene catalyst layer, without using
Graphene film layer transfer producing process, avoid impurity pollution while also reduce the caused film in graphene film layer transfer process
Defect and the uneven stacking of multilayer material, simplify graphene growth processing procedure, are easy to large-scale industrial production.
Step 130, gallium nitride exposed on the surface of graphene mask layer and in the hole of graphene mask layer
The surface Epitaxial growth gallium nitride layer of cushion.
The hole of graphene mask layer 240 as shown in Figure 2 can exposed GaN cushions 220 surface, therefore graphene mask
The hole of floor 240 is follow-up GaN Process window area.In the present embodiment on the surface of graphene mask layer 240 and in stone
The surface Epitaxial growth gallium nitride layer 250 of exposed nitride buffer layer 220 in the hole of black alkene mask layer 240, it is specifically
It is mask with graphene film layer 240, GaN nucleating growths on the surface of graphene mask layer 240 go out the second epitaxial layer of gallium nitride
252, while nucleating growth goes out on the surface of GaN GaN cushions 220 exposed also in the hole of graphene mask layer 240
One epitaxial layer of gallium nitride 251.
Adopted it will be apparent that being much larger than using the nucleation energy between the GaN and graphene mask layer 240 of heteroepitaxial growth
With the nucleation energy between GaN the and GaN cushions 220 of isoepitaxial growth, therefore GaN is on the surface of graphene mask layer 240
The speed of growth is much smaller than the speeds of growth of the GaN in Process window area.Grown as GaN using homoepitaxy in Process window area
When the thickness of first epitaxial layer of gallium nitride 251 exceedes the thickness of graphene mask layer 240, GaN begins to cross growth and and stone
The GaN on the black surface of alkene mask layer 240 merges to form continuous gallium nitride layer 250, i.e. the first epitaxial layer of gallium nitride 251 and second
The merging growth of epitaxial layer of gallium nitride 252 is gallium nitride layer 250, and then gallium nitride layer 250 can be required using continued growth to thickness
Untill thickness, thus gallium nitride film is formed in Semiconductor substrate 210.
Advantage using graphene as mask growing gallium nitride layer is, connected between the carbon atom of graphene it is fairly regular and
Flexible, the lattice mismatch between carbon atom and GaN material is also small (lattice mismatch 3%), can effectively reduce on a semiconductor substrate
The dislocation density of gallium nitride film growth, and single-layer graphene is two-dimensional material, can effectively reduce epitaxial layer of gallium nitride and stone
The low angle grain boundary defect of black alkene mask layer contact portion, mask caused crystal defect in itself is at utmost reduced, improves nitrogen
Change the performance of gallium film；Semiconductor substrate can be selected maturation and use extensive Si (100) crystal plane structure substrate in the present embodiment,
Although cube Si (100) crystal faces and six side GaN (0001) crystal faces have different symmetry, graphene mask layer conduct is used
After mask, hexagoinal lattice and the GaN of graphene have identical symmetry, and GaN molecules can be naturally according to graphene-structured
Growth, GaN (0001) crystal face for making to grow on Si (100) crystal face have good crystal phase structure, improve gallium nitride film
Performance, promote gallium nitride based electronic and optoelectronic device commercialization；Graphene mask layer has nanometer porous gap structure, its hole
For Process window area, GaN Process window area and nitride buffer layer homogenous growth simultaneously also on graphene mask layer it is heterogeneous
Growth, the first epitaxial layer of gallium nitride of homogenous growth and the second epitaxial layer of gallium nitride of Heteroepitaxy merge and intensive interval is interlocked
Growth, forms equally distributed gallium nitride layer, and the gallium nitride material of low dislocation can effectively reduce entirety on graphene mask layer
The dislocation density of gallium nitride film.
The preparation method for the gallium nitride film that the present embodiment provides, using the graphene mask layer with pore structure as covering
Film epitaxial growth of gallium nitride layer；Fairly regular and flexible, the hexagoinal lattice and GaN of graphene are connected between the carbon atom of graphene
With identical symmetry, GaN film can be according to graphene-structured autonomous growth, the lattice between graphene and GaN material
Mismatch is less than 3%, can effectively reduce the dislocation density of gallium nitride film growth on a semiconductor substrate, and single-layer graphene is
Two-dimensional material, it can effectively reduce the low angle grain boundary defect of epitaxial layer of gallium nitride and graphene mask layer contact portion, maximum journey
Degree reduces mask caused crystal defect in itself, and the gallium nitride film formed can be uniformly distributed and with brilliant well
Phase structure, the performance of gallium nitride film is thus improved, promote gallium nitride based electronic and optoelectronic device commercialization.
On the basis of above-mentioned technical proposal, the utility model embodiment two also provides a kind of preparation side of gallium nitride film
Method, the preparation method mainly form gallium nitride film on a semiconductor substrate using chemical vapour deposition technique.In this reference chart 3A
The preparation method that preparation technology flow chart shown in~Fig. 3 E is provided the present embodiment is described in detail, and continues to use Fig. 2 accompanying drawing
Mark.
As shown in Figure 3A, there is provided semi-conductive substrate 210.The Semiconductor substrate 210 optional in the present embodiment serves as a contrast for silicon
Bottom, the indices of crystallographic plane of silicon substrate are (100), and Si (100) manufacturing technology is ripe, be widely used and cost is low.
As shown in Figure 3 B, nitride buffer layer 220 is formed in Semiconductor substrate 210, optional gallium nitride in the present embodiment
The thickness of cushion 220 is less than or equal to 2 μm.17% lattice mismatch and thermal coefficient of expansion between Si substrates and GaN material be present
Mismatch, if the thickness of GaN cushions 220 is thicker, Macrolattice mismatch and coefficient of thermal expansion mismatch can cause big lattice defect and
Dislocation density, and lattice defect is smaller and dislocation density when the thickness of GaN cushions 220 is less than or equal to 2 μm in the present embodiment
It is relatively low, big influence will not be produced to GaN quality of forming film.It should be noted that nitride buffer layer 220 in the present embodiment
Thickness be to be set on the basis of forming more than 5 μm of gallium nitride film.It will be understood by those skilled in the art that gallium nitride is thin
During film thickness difference, the maximum gauge of nitride buffer layer is it can also be provided that difference, such as nitrogen when gallium nitride film is 100 μm
Change the maximum gauge of gallium cushion it can also be provided that 5 μm, without concrete restriction in the utility model.
The specific implementation procedure of formation nitride buffer layer 220 in Semiconductor substrate 210 can be selected in the present embodiment to be included：
Semiconductor substrate 210 is placed in reative cell of the temperature environment more than 900 DEG C, is passed through TMGa (trimethyl gallium) in the reaction chamber
Gas and NH3Gas, current-carrying gas H2Gas, served as a contrast using MOCVD method (MOCVD) in semiconductor
The Epitaxial growth thickness of bottom 210 is less than or equal to 2 μm of nitride buffer layer 220.It will be understood by those skilled in the art that using
When MOCVD techniques form GaN cushions on a si substrate, gallium source includes but is not limited to TMGa, in other alternative embodiments also
Optional gallium source is TEGa (triethyl-gallium)；It is also optional in other alternative embodiments to be formed on a si substrate using other techniques
GaN cushions, corresponding gallium source and nitrogen source etc. change, will not be repeated here and illustrate, any one can be in semiconductor
The technique that GaN cushions are formed on substrate each falls within the scope of protection of the utility model.
As shown in Figure 3 C, the graphene catalyst layer 230 with the first pore structure is formed on nitride buffer layer 220.
The composition material of optional graphene catalyst layer 230 is single metal or alloy, and the composition material of optional graphene catalyst layer 230 is
Any one in Cu, Ni, Pt, Co, Ti and Fe, or, the composition material of graphene catalyst layer 230 include Cu, Ni, Pt, Co,
The alloy of any a variety of compositions in Ti and Fe.It can be selected in the present embodiment in Si base GaN substrates and use chemical vapour deposition technique
A layer graphene Catalytic Layer 230 is deposited, the thickness of the graphene catalyst layer 230 is more than or equal to 0.2nm and is less than or equal to
10nm, graphene catalyst layer is specifically formed using chemical vapour deposition technique on substrate after taking-up substrate from reative cell
230.Wherein 230 non-continuous film forming of graphene catalyst layer, belong to island film or chain film, and the graphene catalyst layer 230 has
Nanometer porous gap structure, its hole are easy to subsequently be used as gallium nitride Process window area.
As shown in Figure 3 D, formed in the graphene catalyst layer 230 with the first pore structure with the second pore structure
Graphene mask layer 240, the first pore structure and the second pore structure are identical.The thickness of optional graphene mask layer 240 is big
In or equal to 0.2nm and it is less than or equal to 2nm.The specific implementation procedure of graphene mask layer 240 is formed in the present embodiment to be included：
The first substrate formed with graphene catalyst layer 230 is placed on into temperature environment to be in 800~1000 DEG C of reative cell, anti-
Answer and carbonaceous gas is passed through in room, there is graphene catalyst layer in the first substrate using Low Pressure Chemical Vapor Deposition (LPCVD)
Growth thickness is more than or equal to 0.2nm and the graphene mask layer 240 less than or equal to 2nm on 230 region, covers graphene
Film layer 240 has and first the second pore structure of pore structure identical.
The region that graphene catalyst layer 230 in the present embodiment only be present can just grow graphene mask layer 240, graphene
Graphene mask layer 240, therefore the pore structure and film layer of graphene mask layer 240 will not be grown in the hole of Catalytic Layer 230
Structure is consistent with graphene catalyst layer 230.240 non-continuous film forming of graphene mask layer, belongs to island film or chain in the present embodiment
Shape film, and the graphene mask layer 240 has nanometer porous gap structure, its hole is easy to subsequently be used as gallium nitride Process window
Area, and the hole can expose the surface of nitride buffer layer 220.
Specifically, the first substrate after deposited graphite alkene Catalytic Layer 230 is put into LPCVD reative cells, while will reaction
Room is warming up to 800~1000 degrees Celsius, and 0.2~2nm stone is grown in the graphene catalyst layer 230 of nanometer porous gap structure
Black alkene mask layer 240.The carbon source for growing graphene mask layer 240 can be carbonaceous gas, such as ethene (C2H4), acetylene
(C2H2), methane (CH4) etc., graphene catalyst layer 230 are that graphene produces catalyst, graphene catalyst layer 230 only be present
Region can just grow graphene mask layer 240, ultimately form the graphene mask layer 240 with nanometer porous gap structure.
The surface of GaN cushions 220 is still exposed in the nanoaperture of graphene mask layer 240, is subsequent reactions window region.The present embodiment
The thickness of middle graphene mask layer 240 is 0.2~2nm, can effectively reduce epitaxial layer of gallium nitride and be contacted with graphene mask layer
Part low angle grain boundary defect, maximum reduce graphene mask layer caused crystal defect in itself.
Graphene (Graphene) is a kind of honeycomb-like two-dimensional nano material of hexangle type being made up of sp2 hydbridized carbon atoms
Material, there is novel two-dimensional material characteristic, high carrier mobility, high conduction performance and high-termal conductivity.Graphene and nitridation
The lattice mismatch of gallium is no more than 3%, while the hexagoinal lattice of graphene has identical symmetry, therefore GaN molecule energy with GaN
It is enough to be grown naturally according to graphene-structured.Use industrialized production graphene film processing procedure in the prior art, from Cu, Ni or
The metallic substrates of the materials such as Fe, chemical vapour deposition technique is used under the process temperatures more than 1000 degrees Celsius, makes carbonaceous gas
In Carbon deposition form graphene layer on the metallic substrate, finally graphene layer is transferred on other substrates.However, shifting
During graphene layer, can there are the pollution of metallic substrates, the diffusion of the metal of such as metallic substrates and residual, then follow-up
When carrying out device fabrication based on graphene layer, the pollution of metal can influence the performance of device, cause the failure of device.In addition, adopt
Operation with graphene layer transfer producing process is relative complex, is not easy to mass produce, and easily cause graphene film defect with
Stack, influence the overall integrity and stability of graphene film.Therefore LPCVD is used in the present embodiment in graphene catalyst layer
Growth in situ graphene mask layer 240 on 230, the problem of without using transfer producing process, avoiding metallic pollution, it is easy to extensive
Production, it will be understood by those skilled in the art that the growth technique of the graphene mask layer 240 can also be applied in other devices
In, it is not limited only to GaN device.
As shown in FIGURE 3 E, it is exposed on the surface of graphene mask layer 240 and in the hole of graphene mask layer 240
Nitride buffer layer 220 surface Epitaxial growth gallium nitride layer 250.It is optional from nitride buffer layer 220 towards semiconductor
Thickness of one side surface of substrate 210 to gallium nitride layer 250 away from a side surface of Semiconductor substrate 210 is more than or equal to 5 μm,
I.e. the thickness of gallium nitride film is more than or equal to 5 μm.
It can be selected on the surface of graphene mask layer 240 and in the hole of graphene mask layer 240 in the present embodiment
The specific implementation procedure of the surface Epitaxial growth gallium nitride layer 250 of exposed nitride buffer layer 220 includes：Will be formed with stone
Second substrate of black alkene mask layer 240 is placed in reative cell of the temperature environment more than 900 DEG C, is passed through TMGa gas in the reaction chamber
Body and NH3Gas, current-carrying gas H2Gas；The surface of exposed nitride buffer layer 220 in the hole of graphene mask layer 240
Upper isoepitaxial growth goes out the first epitaxial layer of gallium nitride 251, the C=C double bonds fracture in graphene mask layer 240 and with TMGa gas
Body and NH3Gas reaction combines to form the second epitaxial layer of gallium nitride 252, the first epitaxial layer of gallium nitride 251 grow and with the second nitrogen
Change gallium epitaxial layer 252 to merge with gallium nitride layer 250 of the epitaxial growth thickness more than or equal to 5 μm.
Specifically, the temperature of reative cell is adjusted in more than 900 DEG C of environment, and TMGa gases and NH3 gases are passed through,
Current-carrying gas is H2 gas, then the C=C double bonds fracture in graphene mask layer 240, and with NH3 and TMGa reaction bondeds using different
Matter epitaxial growth goes out the second epitaxial layer of gallium nitride 252；Meanwhile the nanoaperture of graphene mask layer 240 is as GaN cushions
Process window area, the first epitaxial layer of gallium nitride 251 is gone out using isoepitaxial growth.Because GaN is on the surface of graphene mask layer 240
Nucleation energy be much larger than nucleation energies of the GaN on GaN, therefore the speeds of growth of the GaN in Process window area is much larger than in graphene
The speed of growth on mask layer 240.The thicknesses of layers of the first epitaxial layer of gallium nitride 251 grown in Process window area exceedes graphite
After the thickness of alkene mask layer 240, the first epitaxial layer of gallium nitride 251 will start cross growth, and the of last adjacent reaction window region
One epitaxial layer of gallium nitride 251 and the cross growth of the second epitaxial layer of gallium nitride 252 form continuous GaN layer 250 until merging, after
The continuous gallium nitride film for growing into more than 5 μm.
In the present embodiment on silicon based gallium nitride substrate after deposited metal Catalytic Layer, the growth in situ in LPCVD reative cells
Graphene mask layer, without using existing graphene film layer transfer producing process, metallic pollution is avoided, while reduce in graphene
Caused film defects in film layer transfer process, graphene film layer and the uneven stacking of multilayer material are also avoided, simplifies graphite
Alkene growth process, is easy to large-scale industrial production.
It will be understood by those skilled in the art that nitride buffer layer, graphene catalyst layer, graphene are covered in gallium nitride film
The preparation condition of film layer and gallium nitride layer, technique and parameter etc. are not limited to above-mentioned example, related practitioner can according to product and
Preparation technology and parameter etc. are voluntarily set needed for working condition, without concrete restriction in the utility model.
The preparation method for the gallium nitride film that the present embodiment provides, using the graphene mask layer with pore structure as covering
Film epitaxial growth of gallium nitride layer, the dislocation density of gallium nitride film growth on a semiconductor substrate can be effectively reduced, effectively reduced
Epitaxial layer of gallium nitride and the low angle grain boundary defect of graphene mask layer contact portion, it is caused in itself at utmost to reduce mask
Crystal defect, and the gallium nitride film formed can be uniformly distributed and have good crystal phase structure, thus improve nitridation
The performance of gallium film, promote gallium nitride based electronic and optoelectronic device commercialization.
The utility model embodiment three additionally provides a kind of gallium nitride film, and the gallium nitride film is using above-mentioned any implementation
Prepared by the preparation method described in example, the gallium nitride film includes：Semiconductor substrate, formed with nitridation in the Semiconductor substrate
Gallium cushion；Graphene catalyst layer with the first pore structure is sequentially formed with nitride buffer layer and with the second hole
The graphene mask layer of structure, the first pore structure and the second pore structure are identical；On the surface of graphene mask layer and stone
The surface Epitaxial growth of exposed nitride buffer layer has gallium nitride layer in the hole of black alkene mask layer.The nitridation of the present embodiment
Gallium film is applied to a variety of photoelectric devices, power electronic devices, and do not limit gallium nitride film in the utility model applies model
Enclose.
As shown in figure 4, the structural representation of the graphene film provided for the utility model embodiment four, the present embodiment
Technical scheme is applied to the situation that growth in situ on a semiconductor substrate goes out the graphene film of high quality.What the present embodiment provided
Graphene film includes：Semiconductor substrate 310；Formed with the graphene with the first pore structure in Semiconductor substrate 310
Catalytic Layer 320；Formed with the graphene layer 330 with the second pore structure, the first pore structure in graphene catalyst layer 320
It is identical with the second pore structure.
Fig. 5 is the flow chart of the preparation method of the graphene film shown in Fig. 4, and the present embodiment is provided with reference to Fig. 4 and Fig. 5
Graphene film be described in detail.
The preparation method for the graphene film that the present embodiment provides, specifically comprises the following steps：
Step 410, provide semi-conductive substrate.
Optional Semiconductor substrate is silicon substrate (Si), and the indices of crystallographic plane of silicon substrate are (100) or (111).It is optional at other
Semiconductor substrate can be the silicon substrate of silicon carbide substrates or other indices of crystallographic plane in embodiment, and semiconductor serves as a contrast in the utility model
Bottom can be any one existing known Semiconductor substrate for can be used for preparing film, such as sapphire etc., in this practicality
Without concrete restriction in new.
Step 420, the graphene catalyst layer with the first pore structure is formed on a semiconductor substrate.
The effect of graphene catalyst layer is to be easy to growth in situ graphene layer in the present embodiment, and graphene catalyst layer has
First pore structure, the hole of graphene catalyst layer directly exposes Semiconductor substrate, and graphene catalyst layer only be present
Region can just grow graphene layer, it is clear that graphene layer will not be grown in the hole of graphene catalyst layer.Have in the present embodiment
The graphene catalyst layer of first pore structure not continuous film forming, the film layer structure of optional graphene catalyst layer is island film or chain
Shape film, the pore structure of graphene catalyst layer is nanometer porous gap structure, and hole is uniformly distributed and is nano-scale dimension.
The composition material of optional graphene catalyst layer includes any in Cu, Ni, Pt, Co, Ti and Fe in the present embodiment
One kind, or, the composition material of graphene catalyst layer includes the alloy of any a variety of compositions in Cu, Ni, Pt, Co, Ti and Fe,
I.e. graphene catalyst layer is metal catalytic layer, and above-mentioned metal or alloy is the conventional catalysis material of graphene.People in the art
Member is it is appreciated that the composition material of graphene catalyst layer can be existing any one graphene catalysis material in the utility model
Material, is not limited to above-mentioned example.
Exemplary, it is optional that graphene catalyst layer is formed using chemical vapour deposition technique on a semiconductor substrate.But this reality
The method to form graphene catalyst layer with not limiting in new.The region just meeting of graphene catalyst layer in the present embodiment only be present
Graphene layer is grown, i.e. graphene catalyst layer is the production catalyst of graphene layer.
Step 430, in graphene catalyst layer formed with the second pore structure graphene layer, the first pore structure and
Second pore structure is identical.
Graphene layer is grown in the Semiconductor substrate with graphene catalyst layer in the present embodiment.Graphene catalyst layer is simultaneously
Non- continuous film forming, and the region that graphene catalyst layer only be present can just grow graphene layer, the hole institute of graphene catalyst layer
Graphene layer will not be grown in region, therefore graphene catalyst layer and graphene layer have completely the same pore structure, i.e. stone
First pore structure of black alkene Catalytic Layer is identical with the second pore structure of graphene layer.With the film layer structure of graphene catalyst layer
Corresponding with pore structure, graphene layer not continuous film forming, the film layer structure of optional graphene layer is island film or chain film, stone
The pore structure of black alkene layer is nanometer porous gap structure, and hole is uniformly distributed and is nano-scale dimension.The composition of graphene layer
Material is carbon material, and Low Pressure Chemical Vapor Deposition growth in situ graphite in graphene catalyst layer can be used in the present embodiment
Alkene layer.But the technique that graphene layer is grown in graphene catalyst layer is not particularly limited in the utility model.
Exemplary, the thickness of optional graphene catalyst layer is more than or equal to 0.2nm and is less than or equal to 10nm, optional stone
The thickness of black alkene layer is more than or equal to 0.2nm and is less than or equal to 2nm.
Exemplary, forming the specific implementation procedure of graphene layer includes：By the semiconductor formed with graphene catalyst layer
Substrate is placed on temperature environment and is in 800~1000 DEG C of reative cell, carbonaceous gas is passed through in the reaction chamber, using low pressure
Learn vapour deposition process and graphene layer is grown in graphene catalyst layer.Specifically, the carbon source of growth graphene layer can be carbon containing
Gas, such as ethene (C2H4), acetylene (C2H2), methane (CH4), nanoscale graphite alkene layer can be formed using LPCVD.This area
Technical staff is appreciated that the growth technique of the graphene layer may be applied not only in the device using graphene film, moreover it is possible to
Enough apply in other of graphene film device.
It will be understood by those skilled in the art that preparation condition and parameter of graphene catalyst layer and graphene layer etc. are not limited to
Above-mentioned example, related practitioner can voluntarily choose preparation condition and parameter etc. according to needed for product and working condition, in this reality
With in new without concrete restriction.
It is existing to use industrialized production graphene film processing procedure, from the metallic substrates of the materials such as Cu, Ni or Fe, 1000
Chemical vapour deposition technique is used under process temperatures more than degree Celsius, the Carbon deposition in carbonaceous gas is formed on the metallic substrate
Graphene layer, finally graphene layer is transferred on other substrates.However, during graphene layer is shifted, there can be gold
Belong to the pollution of substrate, the diffusion of the metal of such as metallic substrates and residual, then device fabrication is subsequently being carried out based on graphene layer
When, the pollution of metal can influence the performance of device, cause the failure of device.In addition, the operation using graphene layer transfer producing process
It is relative complex, it is not easy to mass produce, and easily cause graphene film defect and stack, influence the entirety of graphene film
Integrality and stability.And existing graphene film not only needs to use transfer producing process, it is also necessary to use when applying as mask
Processing procedure is etched, i.e., complete graphene film is performed etching to form required graphene mask film, complex procedures.
Compared with prior art, after forming graphene catalyst layer on a semiconductor substrate in the present embodiment, urged in graphene
Change growth in situ graphene layer on layer, i.e., growth in situ goes out the graphene film with pore structure on a semiconductor substrate, should
Graphene film can be complete without being formed without using existing graphene film transfer producing process directly as mask application
Processing procedure is performed etching after film layer again, saves process；And manufacturing process is simple and avoids impurity pollution, also reduces simultaneously
Caused film defects and stacking in graphene film transfer process, simplify graphene film growth process, suitable for big
Large-scale production, improve the overall integrity and stability of graphene film.
Pay attention to, above are only preferred embodiment of the present utility model and institute's application technology principle.Those skilled in the art's meeting
Understand, the utility model is not limited to specific embodiment described here, can carried out for a person skilled in the art various bright
Aobvious change, readjust and substitute without departing from the scope of protection of the utility model.Therefore, although passing through above example
The utility model is described in further detail, but the utility model is not limited only to above example, is not departing from
In the case that the utility model is conceived, other more equivalent embodiments can also be included, and the scope of the utility model is by appended
Right determine.
Claims (7)
- A kind of 1. gallium nitride film, it is characterised in that including：Semiconductor substrate, formed with nitride buffer layer in the Semiconductor substrate；Graphene catalyst layer with the first pore structure is sequentially formed with the nitride buffer layer and with the second hole The graphene mask layer of structure, first pore structure are identical with second pore structure；Exposed gallium nitride buffering on the surface of the graphene mask layer and in the hole of the graphene mask layer The surface Epitaxial growth of layer has gallium nitride layer.
- 2. gallium nitride film according to claim 1, it is characterised in that the Semiconductor substrate is silicon substrate, the silicon The indices of crystallographic plane of substrate are (100) or (111).
- 3. gallium nitride film according to claim 1, it is characterised in that the thickness of the nitride buffer layer is less than or waited In 2 μm；The thickness of the graphene catalyst layer is more than or equal to 0.2nm and is less than or equal to 10nm；The thickness of the graphene mask layer is more than or equal to 0.2nm and is less than or equal to 2nm；Partly led away from described to the gallium nitride layer side surface from the nitride buffer layer towards the Semiconductor substrate The thickness of one side surface of body substrate is more than or equal to 5 μm.
- 4. gallium nitride film according to claim 1, it is characterised in that the composition material of the graphene catalyst layer includes Any one in Cu, Ni, Pt, Co, Ti and Fe, or, the composition material of the graphene catalyst layer include Cu, Ni, Pt, The alloy of any a variety of compositions in Co, Ti and Fe.
- A kind of 5. graphene film, it is characterised in that including：Semiconductor substrate；On the semiconductor substrate formed with the graphene catalyst layer with the first pore structure；Formed with the graphene layer with the second pore structure, first pore structure and institute in the graphene catalyst layer It is identical to state the second pore structure.
- 6. graphene film according to claim 5, it is characterised in that the composition material of the graphene catalyst layer includes Any one in Cu, Ni, Pt, Co, Ti and Fe, or, the composition material of the graphene catalyst layer include Cu, Ni, Pt, The alloy of any a variety of compositions in Co, Ti and Fe.
- 7. graphene film according to claim 5, it is characterised in that the thickness of the graphene catalyst layer is more than or waited In 0.2nm and it is less than or equal to 10nm；The thickness of the graphene layer is more than or equal to 0.2nm and is less than or equal to 2nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106960781A (en) * | 2017-03-28 | 2017-07-18 | 刘志斌 | A kind of gallium nitride film and preparation method thereof and graphene film and preparation method thereof |
| CN112864001A (en) * | 2020-12-31 | 2021-05-28 | 镓特半导体科技（上海）有限公司 | Semiconductor structure, self-supporting gallium nitride layer and preparation method thereof |
| CN115832137A (en) * | 2023-02-16 | 2023-03-21 | 江西乾照光电有限公司 | LED epitaxial wafer, epitaxial growth method and LED chip |
-
2017
- 2017-03-28 CN CN201720310168.1U patent/CN207116374U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106960781A (en) * | 2017-03-28 | 2017-07-18 | 刘志斌 | A kind of gallium nitride film and preparation method thereof and graphene film and preparation method thereof |
| CN112864001A (en) * | 2020-12-31 | 2021-05-28 | 镓特半导体科技（上海）有限公司 | Semiconductor structure, self-supporting gallium nitride layer and preparation method thereof |
| CN115832137A (en) * | 2023-02-16 | 2023-03-21 | 江西乾照光电有限公司 | LED epitaxial wafer, epitaxial growth method and LED chip |
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