CN114678257A - Nitride template based on metal substrate and preparation method and application thereof - Google Patents
Nitride template based on metal substrate and preparation method and application thereof Download PDFInfo
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
- H01L21/0237—Materials
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/04—Pattern deposit, e.g. by using masks
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
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- H01L21/02518—Deposited layers
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- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
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Abstract
The invention provides a nitride template based on a metal substrate, which relates to the field of semiconductor technology and communication and comprises the following components: the nitride epitaxial layer is formed by a metal substrate, a two-dimensional material film, an inert material pattern mask layer and a nitride epitaxial layer; the surface of the two-dimensional material film is subjected to activation treatment to provide nucleation sites for the growth of a nitride material and inhibit the interface reaction in the high-temperature epitaxial process; the inert material pattern mask layer realizes selective area epitaxy of the nitride material, further realizes transverse over-epitaxial growth, reduces dislocation density in the nitride epitaxial layer and improves the crystal quality of the epitaxial layer. The invention also provides a preparation method and application of the template, and the composite metal substrate structure of the metal substrate/two-dimensional material film/inert material pattern mask layer is adopted, so that the direct high-temperature epitaxial growth of high-quality and stress-free nitride materials can be realized, the template has higher expandability, and the template is suitable for deep ultraviolet LEDs devices and the epitaxy and devices of second-generation semiconductor materials such as GaAs, InP and the like.
Description
Technical Field
The invention relates to the field of semiconductor technology and communication, in particular to a nitride template based on a metal substrate and a preparation method and application thereof.
Background
At present, the selectivity of a nitride material heteroepitaxial substrate is low, and the nitride material heteroepitaxial substrate is mainly a sapphire material. A large dislocation density and high residual stress inevitably occur in the nitride epitaxial layer against the lattice mismatch and the difference in thermal expansion coefficient inherent between the sapphire substrate and the nitride material. In addition, the sapphire substrate is brittle and fragile, has strong rigidity, and is completely not suitable for the flexible application of nitride-based devices; more importantly, sapphire has poor thermal conductivity (25W/mK thermal conductivity), which causes heat accumulation and ineffective release of high-power nitride-based devices, and affects the lifetime and stability of the devices. Generally, in order to meet the heat dissipation requirement of high-power nitride-based devices, it is necessary to remove or thin the sapphire substrate by laser lift-off or mechanical grinding, and then transfer and compound the epitaxial layer structure of the device with high thermal conductivity materials (such as metal and thermal conductive ceramic) to reduce the heat accumulation effect. However, this inevitably makes the device fabrication process more complicated, increasing the manufacturing cost; meanwhile, the mechanical damage in the substrate stripping process also causes the performance reduction and the yield reduction of the device.
The metal material has excellent ductility, and the epitaxial substrate serving as a nitride material is expected to expand the application potential of the device in the aspect of flexibility. In addition, compared with a sapphire substrate, the thermal conductivity (Mo: 138W/mK) of the metal is obviously improved, and the problem of heating of the device under the condition of high-current injection is solved. Therefore, how to realize the epitaxy of high-quality nitride materials and high-performance device structures on metal substrates has very important significance and value. However, due to the chemical activity of metal materials, MBE and MOCVD-based high temperature epitaxial growth processes of nitrides cause strong chemical reactions between the metal substrate and the epitaxial layer, resulting in dopant desorption and phase separation of the nitride materials. Therefore, the epitaxy of nitride materials on the existing metal substrate usually adopts a low-temperature deposition process such as Pulsed Laser Deposition (PLD) to avoid the above chemical reaction; however, the crystal quality of the epitaxial material is low because the calcium deposition mode has a low temperature and cannot provide sufficient reaction energy for the growth of high-quality nitride materials. Recently, related researches propose that the interface reaction can be inhibited to a certain extent by using graphene as a buffer insertion layer and realizing the epitaxy of a nitride material on a metal substrate, but the crystal quality of the material still needs to be further improved.
Therefore, there is a need to effectively suppress the formation of stress and defects during nitride epitaxy by precise design of the epitaxial substrate structure, and to achieve the fabrication of high quality, stress-free nitride materials and high performance devices.
Disclosure of Invention
In view of the above, the present invention provides a metal substrate-based nitride template, and a preparation method and an application thereof, which solve or at least partially solve the technical defects in the prior art.
In order to realize the purpose, the invention adopts the following technical scheme:
a metal substrate based nitride template comprising:
a metal substrate;
a two-dimensional material film located on one side of the metal substrate;
the inert material pattern mask layer is positioned on the side face, far away from the metal substrate, of the two-dimensional material film;
the nitride epitaxial layer is positioned on the side face, far away from the metal substrate, of the inert material pattern mask layer;
the surface of the two-dimensional material film is subjected to activation treatment to provide nucleation sites for the growth of a nitride material, and the two-dimensional material film is also used for inhibiting the interface reaction in the high-temperature epitaxial process; the inert material pattern mask layer realizes selective area epitaxy of the nitride material, further realizes transverse over-epitaxial growth, reduces dislocation density in the nitride epitaxial layer and improves the crystal quality of the epitaxial layer.
Furthermore, the material of the metal substrate is any one of Mo, W, V, Cr and Ta.
Furthermore, the two-dimensional material film is made of graphene, h-BN and WS2、WSe2、MoS2、MoSe2Any one of them.
Further, the inert material pattern mask layer is made of SiO2Or Si3N4。
The invention also provides a preparation method of the nitride template based on the metal substrate, which comprises the following steps:
s1 preparation of the metal substrate/two-dimensional material film double-layer structure: directly epitaxially growing the two-dimensional material film on the metal substrate by adopting a CVD method, or growing the two-dimensional material film on a catalytic metal Ni or Cu foil by adopting the CVD method, and transferring the two-dimensional material film to the metal substrate by a wet transfer process;
preparing an inert material pattern mask layer by S2: depositing an inert film with a certain thickness on the surface of the two-dimensional material film, and preparing a mask pattern on the inert film;
s3, activation treatment of the two-dimensional material film: firstly, carrying out plasma treatment, and then carrying out high-temperature nitridation treatment on the two-dimensional material film based on an MBE (molecular beam epitaxy) or MOCVD (metal organic chemical vapor deposition) method to form effective doping of N atoms so as to form a metal composite substrate;
Preparation of S4 nitride epitaxial layer: and firstly, carrying out plasma treatment, and then epitaxially growing a nitride material on the metal composite substrate based on an MBE (molecular beam epitaxy) and MOCVD (metal organic chemical vapor deposition) method.
Further, in step S1, when the two-dimensional material film is made of graphene, CH is adopted4Or C2H4As a precursor material;
when the two-dimensional material film is made of h-BN, NH is adopted3-BH3As a precursor material;
the two-dimensional material film is made of WS2、WSe2、MoS2、MoSe2Any one of the two is obtained by adopting the direct chemical reaction of the metal substrate Mo or W and the simple substance S or Se, and the growth temperature is set to 800-1200 ℃.
Further, in step S2, the method for preparing the mask pattern on the inert thin film is any one of photolithography, nanoimprint lithography, and focused ion beam etching;
the size, shape and period of the mask pattern can be designed, and the thickness of the inert film can be designed.
Further, in step S2, preparing a photoresist mask pattern on the inert thin film by using a photolithography process, then removing the inert thin film in a region without a photoresist coverage area by using a reactive ion etching method and controlling the etching thickness to be smaller than the thickness of the inert thin film, then removing the remaining inert thin film in the photoresist coverage area by using an HF solution through chemical etching, and finally removing the photoresist mask by using an organic solvent, wherein the two-step removal process can avoid damage of the two-dimensional material thin film caused by direct reactive ion etching;
Wherein, the etching thickness of the inert film in the area without the photoresist covering is larger than the residual thickness of the inert film.
The invention also provides a nitride template based on the metal substrate, which is applied to AlGaN-based deep ultraviolet LEDs, and the nitride template based on the metal substrate is used as a substrate to sequentially extend an n-AlGaN electron transmission layer, an AlGaN multi-quantum well structure with alternating high and low Al components and a p-AlGaN hole transmission layer.
The invention also provides a nitride template based on the metal substrate, which is applied to the epitaxy and the device of the GaAs or InP second-generation semiconductor material, wherein the nitride template based on the metal substrate is used as the substrate to grow the epitaxy material or the device;
the device is any one of LEDs, a photoelectric detector and an HEMT.
According to the nitride template based on the metal substrate and the preparation method thereof, a composite metal substrate structure of the metal substrate/the two-dimensional material film/the inert material pattern mask layer is adopted, the metal substrate is beneficial to solving the heating problem of a device under the condition of high current injection, and the heat dissipation capability is improved; the two-dimensional material film can effectively inhibit the interface reaction in the high-temperature epitaxy process; the inert material pattern mask layer is used for realizing the transverse over-epitaxial growth of the nitride material and improving the crystal quality of the epitaxial layer. The two-dimensional material film is activated to increase the difference of the nitride nucleation energy barrier on the two-dimensional material film and the inert material pattern mask layer, and the selectivity of the nitride nucleation growth site is improved; can realize direct high-temperature epitaxial growth of high-quality and stress-free nitride materials. The invention has higher expandability, is suitable for the application of deep ultraviolet LEDs (light emitting diodes) devices, is also suitable for the epitaxy and device application of second-generation semiconductor materials such as GaAs, InP and the like, and comprises but is not limited to LEDs, a photoelectric detector, an HEMT and the like; the method is proposed based on the existing semiconductor device process technology and is suitable for inch-scale production technology.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a metal substrate-based nitride template according to the present invention;
FIG. 2 is a schematic process flow diagram of a method for fabricating a metal substrate-based nitride template according to the present invention;
fig. 3 is a schematic structural view of AlGaN-based deep ultraviolet LEDs according to embodiment 2 of the present invention;
description of reference numerals: 1-a metal substrate; 2-a two-dimensional material film; 3-inert material pattern mask layer; a 4-nitride epitaxial layer.
Detailed Description
Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are exemplary only for the purpose of illustrating the invention and are not to be construed as limiting the application.
The invention provides a nitride template based on a metal substrate, as shown in figure 1, comprising:
a metal substrate 1;
a two-dimensional material film 2 which is positioned on one side of the metal substrate;
the inert material pattern mask layer 3 is positioned on the side face, far away from the metal substrate, of the two-dimensional material film;
the nitride epitaxial layer 4 is positioned on the side face, far away from the metal substrate, of the inert material pattern mask layer;
the surface of the two-dimensional material film 2 is subjected to activation treatment to provide nucleation sites for the growth of a nitride material, and the two-dimensional material film 2 is also used for inhibiting an interface reaction in a high-temperature epitaxial process; the inert material pattern mask layer 3 realizes selective area epitaxy of nitride materials, further realizes transverse over-epitaxial growth, reduces dislocation density in the nitride epitaxial layer 4, and improves epitaxial layer crystal quality.
The material of the metal substrate 1 is a high melting point metal material, including but not limited to Mo, W, V, Cr, and Ta, and the metal substrate 1 is used as an initial supporting substrate.
The two-dimensional material film 2 is made of a low-dimensional material with strong chemical/thermal stability, such as graphene, h-BN and Transition Metal Dichalcogenides (TMDs), and the two-dimensional material film 2 serves as a buffer insertion layer. Because the surface of the two-dimensional material has no dangling bond and has stable structure, the interface reaction in the high-temperature growth process of the nitride can be avoided.
Based on the catalytic activity of the metal material, a Chemical Vapor Deposition (CVD) method is adopted to directly epitaxially grow a two-dimensional material film 2 on the metal substrate 1. For graphene, CH is employed4Or C2H4As a precursor material; H-BN adopts ammonia borane (NH)3-BH3) As a precursor material; TMDs can be obtained by direct chemical reaction of metal substrate with elemental S or Se to obtain WS2/WSe2And MoS2/MoSe2The growth temperature of the two-dimensional material is set at 800-1200 ℃.
In addition, for the two-dimensional material film 2 grown by CVD on the traditional catalytic metal Ni and Cu foils, the two-dimensional material can be transferred to the metal supporting substrate 1 such as Mo, W and the like by a wet transfer process, so that the construction of a metal substrate/two-dimensional material film double-layer structure is realized.
The material of the inert material pattern mask layer 3 includes but is not limited to SiO2And Si3N4And the like, realizing the epitaxy of the nitride material in a selected area on the surface of the two-dimensional material film 2, and reducing the dislocation density in the epitaxial nitride material by combining a transverse over-epitaxy technology.
The invention also provides a preparation method of the nitride template based on the metal substrate, the process flow schematic diagram of which is shown in fig. 2, and the preparation method comprises the following steps:
s1 preparation of the metal substrate/two-dimensional material film double-layer structure: directly epitaxially growing the two-dimensional material film 2 on the metal substrate 1 by adopting a CVD method, or growing the two-dimensional material film 2 on a catalytic metal Ni or Cu foil by adopting the CVD method, and transferring the two-dimensional material film to the metal substrate 1 by a wet transfer process;
S2 preparation of inert material pattern mask layer 3: depositing an inert film with a certain thickness on the surface of the two-dimensional material film 2, and then preparing a mask pattern on the inert film;
s3, activation treatment of the two-dimensional material film: performing high-temperature nitridation treatment on the two-dimensional material film 2 based on an MBE (molecular beam epitaxy) or MOCVD (metal organic chemical vapor deposition) method to form effective doping of N atoms and form a metal composite substrate;
preparation of nitride epitaxial layer 4 of S4: and epitaxially growing a nitride material on the metal composite substrate based on MBE and MOCVD.
In step S2, the method for preparing the mask pattern on the inert thin film is flexible and various, and may be any one of photolithography, nanoimprint lithography, focused ion beam etching, and the like; the geometric parameters such as the size, the shape, the period and the like of the mask pattern are flexible and adjustable, and the thickness of the inert film can be properly adjusted according to actual requirements.
For example: preparing a photoresist mask pattern on the inert film by adopting a photoetching process, removing the inert film in a region without photoresist coverage by utilizing a reactive ion etching method and controlling the etching thickness to be smaller than the thickness of the inert film, then removing the rest inert film in the region covered by the photoresist by adopting HF solution chemical corrosion, avoiding the damage of direct reactive ion etching to the two-dimensional material film by adopting a two-step removing process, and finally removing the photoresist mask by adopting an organic solvent; wherein, the etching thickness of the inert film in the area without the photoresist covering is larger than the residual thickness of the inert film.
In step S3, the unprocessed two-dimensional material film has a complete molecular structure and no dangling bond structure outside the surface, and is difficult to provide nucleation sites for the epitaxy of the nitride material, so that the plasma treatment is firstly adopted to destroy chemical bonds on the surface of the two-dimensional material to a certain extent to form a dangling bond structure, and then the high-temperature nitridation treatment based on MBE or MOCVD is carried out to form effective doping of N atoms, thereby improving the reactivity, and serving as the nucleation sites for the subsequent growth of the nitride material.
In step S4, a nitride material is epitaxially grown on the metal composite substrate based on MBE and MOCVD. The activated two-dimensional material film 2 has higher reaction activity compared with SiO2Or Si3N4And (3) waiting for the inert film, the nitride material preferentially nucleates and grows on the two-dimensional material film 2, and selective area epitaxy of the nitride material is realized. In addition, the lateral growth of the nitride material is improved by regulating and controlling the growth process parameters (such as growth temperature, V/V, ammonia pulse method and the like) in the epitaxial process of the nitride materialThe long speed promotes the effective combination of the epitaxial layer films, namely, the transverse over-epitaxial process is realized. In the process of lateral epitaxial merging of the nitride materials, the dislocation lines bend towards the merging direction and are annihilated, and further the dislocation density in the nitride epitaxial layer is effectively reduced.
The invention also provides an application of the nitride template based on the metal substrate in AlGaN-based deep ultraviolet LEDs, which adopts the nitride template based on the metal substrate as a substrate to sequentially extend an n-AlGaN electron transmission layer, an AlGaN multi-quantum well structure with high and low Al components alternating and a p-AlGaN hole transmission layer. The thickness, material composition and doping of each functional layer of the deep ultraviolet LED device are properly designed by combining the advantages of a nitride template based on a metal substrate in the aspect of heat dissipation. The preparation of the deep ultraviolet LEDs can adopt the traditional semiconductor device process, and mainly comprises the steps of etching the device table top and depositing a metal electrode. The invention has higher expandability, and is also suitable for the epitaxy and device application of second generation semiconductor materials such as GaAs, InP and the like, including but not limited to LEDs, photoelectric detectors, HEMT and the like.
Example 1
The AlN template based on the metal substrate is prepared by the following steps:
step S1: a2 inch double-sided polished metal Mo substrate 1 is adopted, the thickness is 230 μm, and the root-mean-square roughness of the surface is lower than 2 nm. Placing the metal Mo substrate 1 in a high-temperature area of a dual-temperature area CVD device, wherein the set temperature is 950 ℃; s powder is placed in a low-temperature area, and the set temperature is 140 ℃. Ar as carrier gas, H 2Providing a reducing atmosphere, directly reacting the simple substance S with the metal Mo substrate 1 to form two-dimensional MoS on the surface layer2And (3) setting the S reaction time of the high-temperature section for about 30-60min for the film 2.
Step S2: in Mo Metal substrate/two-dimensional MoS2Depositing SiO with the thickness of 20-50nm on the film2The film is deposited by PECVD. Positive photoresist process based on AZ5214E photoresist on SiO2The film is prepared into a corresponding photoresist mask pattern, and the preferential pattern is a round hole with the diameter of 500nm and the period of 1 mu m. Further, reactive ion etching is used to remove SiO with sufficient thickness (10-40nm)2A thin film, reserving a residual thickness of about 10 nm; adopts 10 percentVolume fraction of HF solution to remove the remaining 10nm SiO2Film, can effectively avoid over-etching of reactive ion etching to two-dimensional MoS2Destruction of the membrane 2. Finally, removing the photoresist mask pattern in a hot acetone solvent at 80 ℃ to obtain the Mo metal substrate/two-dimensional MoS2Inert SiO on thin films2 Patterned mask layer 3.
Step S3: based on air (the main component being O)2And N2) Introduced into a plasma cleaner, and the etching treatment is not carried out by inert SiO2Two-dimensional MoS covered by graphic mask layer 32The film is prepared under the following treatment conditions: the air flow is 50sccm, the power is 30 percent, the processing time is 30s, and the two-dimensional MoS can be ensured 2On the premise that the main molecular structure of the film 2 is complete, the optimal subsequent doping effect is obtained.
Step S4: placing the metal composite substrate structure in MOCVD, introducing NH of 5000sccm3And activating at 950 ℃ for 10min to form uniform N atom doping and provide nucleation sites for the subsequent AlN material epitaxy. Introducing TMAl of 70sccm and NH of 500-3AlN epitaxial layers 4 having a thickness of about 5 μm were epitaxially grown as Al sources and N sources, respectively. Wherein, due to inert SiO2The inert property of the pattern mask layer 3 can not realize the nucleation growth of AlN, and the whole epitaxial process presents a transverse over-epitaxial growth mode.
Example 2
An AlGaN-based deep ultraviolet led device, as shown in fig. 3, is prepared as follows:
based on the AlN template of the metal substrate prepared in example 1, device function layers of deep ultraviolet LEDs, such as an n-AlGaN electron transport layer, an AlGaN multiple quantum well structure with alternating high and low Al components, a p-AlGaN hole transport layer, and the like, are sequentially extended. Wherein the thickness of the n-AlGaN layer is 400-500nm, and the doping concentration of Si is 5 multiplied by 108/cm3(ii) a The quantum well layer is an AlGaN multi-quantum well layer with alternating high and low Al components, the well thickness is 2nm, and the mass fraction of the Al component is 50%; the barrier thickness is 10nm, and the mass fraction of the Al component is 60%; the thickness of the p-AlGaN layer is 50-100nm, and the Mg doping concentration is 1 multiplied by 10 8/cm3. Respectively preparing N on the upper and lower sides of the table-board based on photoetching plus lift-off processi/Au and Ti/Al are used as the N electrode and the P electrode of the device.
However, the mesa structure of the deep ultraviolet LEDs is prepared based on the conventional semiconductor device process, and the specific process is as follows: deposition of 500nm SiO on deep ultraviolet LEDs epitaxial wafer based on PECVD2As a mask layer, etching on SiO by photoetching process and reactive ion etching2Preparing a mask of a device mesa on the mask layer, etching on the deep ultraviolet LEDs to form a mesa structure based on inductively coupled plasma etching, wherein the size of the mesa prepared at the position is 100 multiplied by 100 mu m2Is square. Conventional processes expose the n-AlGaN electron transport layers of deep ultraviolet LEDs.
According to the nitride template based on the metal substrate and the preparation method thereof, a composite metal substrate structure of the metal substrate/the two-dimensional material film/the inert material pattern mask layer is adopted, the metal substrate is beneficial to solving the heating problem of a device under the condition of high current injection, and the heat dissipation capability is improved; the two-dimensional material film can effectively inhibit the interface reaction in the high-temperature epitaxial process; the inert material pattern mask layer is used for realizing the transverse over-epitaxial growth of the nitride material and improving the crystal quality of the epitaxial layer. The two-dimensional material film is activated to increase the difference of the nitride nucleation energy barrier on the two-dimensional material film and the inert material pattern mask layer, and the selectivity of the nitride nucleation growth site is improved; can realize direct high-temperature epitaxial growth of high-quality and stress-free nitride materials. The invention has higher expandability, is suitable for the application of deep ultraviolet LEDs (light emitting diodes) devices, is also suitable for the epitaxy and device application of second-generation semiconductor materials such as GaAs, InP and the like, and comprises but is not limited to LEDs, a photoelectric detector, an HEMT and the like; the method is proposed based on the existing semiconductor device process technology and is suitable for inch-scale production technology.
The foregoing is only a partial embodiment of the present application, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the principle of the present application, and these modifications and decorations should also be regarded as the protection scope of the present application.
Claims (10)
1. A metal substrate based nitride template, comprising:
a metal substrate;
a two-dimensional material film located on one side of the metal substrate;
the inert material pattern mask layer is positioned on the side face, far away from the metal substrate, of the two-dimensional material film;
the nitride epitaxial layer is positioned on the side face, far away from the metal substrate, of the inert material pattern mask layer;
the surface of the two-dimensional material film is subjected to activation treatment to provide nucleation sites for the growth of a nitride material, and the two-dimensional material film is also used for inhibiting the interface reaction in the high-temperature epitaxial process; the inert material pattern mask layer realizes selective area epitaxy of the nitride material, further realizes transverse over-epitaxial growth, reduces dislocation density in the nitride epitaxial layer and improves the crystal quality of the epitaxial layer.
2. The metal substrate-based nitride template according to claim 1, wherein the metal substrate is made of any one of Mo, W, V, Cr and Ta.
3. The metal substrate-based nitride template of claim 2, wherein the two-dimensional material film is made of graphene, h-BN, WS2、WSe2、MoS2、MoSe2Any one of them.
4. The metal substrate-based nitride template of claim 1, wherein the inert material patterned mask layer is made of SiO2Or Si3N4。
5. A method for preparing a metal substrate based nitride template according to any of claims 1-4, comprising the steps of:
s1 preparation of the metal substrate/two-dimensional material film double-layer structure: directly epitaxially growing the two-dimensional material film on the metal substrate by adopting a CVD method, or growing the two-dimensional material film on a catalytic metal Ni or Cu foil by adopting the CVD method, and transferring the two-dimensional material film to the metal substrate by a wet transfer process;
preparing an inert material pattern mask layer by S2: depositing an inert film with a certain thickness on the surface of the two-dimensional material film, and preparing a mask pattern on the inert film;
s3, activation treatment of the two-dimensional material film: firstly, carrying out plasma treatment, and then carrying out high-temperature nitridation treatment on the two-dimensional material film based on an MBE (molecular beam epitaxy) or MOCVD (metal organic chemical vapor deposition) method to form effective doping of N atoms so as to form a metal composite substrate;
Preparation of S4 nitride epitaxial layer: and epitaxially growing a nitride material on the metal composite substrate based on MBE and MOCVD.
6. The method for preparing a nitride template based on a metal substrate according to claim 5, wherein in step S1, CH is adopted when the material of the two-dimensional material film is graphene4Or C2H4As a precursor material;
when the two-dimensional material film is made of h-BN, NH is adopted3-BH3As a precursor material;
the two-dimensional material film is made of WS2、WSe2、MoS2、MoSe2Any one of the two is obtained by adopting the direct chemical reaction of the metal substrate Mo or W and the simple substance S or Se, and the growth temperature is set to 800-1200 ℃.
7. The method of claim 5, wherein the step S2 of forming the mask pattern on the inert thin film is any one of photolithography, nanoimprinting, and focused ion beam etching;
the size, shape and period of the mask pattern can be designed, and the thickness of the inert film can be designed.
8. The method for preparing a nitride template based on a metal substrate according to claim 7, wherein in step S2, a photoresist mask pattern is prepared on the inert thin film by using a photolithography process, then the inert thin film without a photoresist coverage area is removed by using a reactive ion etching method and the etching thickness is controlled to be smaller than the thickness of the inert thin film, then the remaining inert thin film in the photoresist coverage area is removed by using an HF solution for chemical etching, the damage of the two-dimensional material thin film by direct reactive ion etching can be avoided by using a two-step removal process, and finally the photoresist mask is removed by using an organic solvent;
Wherein, the etching thickness of the inert film in the area without the photoresist covering is larger than the residual thickness of the inert film.
9. The application of the nitride template based on the metal substrate in the AlGaN-based deep ultraviolet LEDs is characterized in that the nitride template based on the metal substrate in any one of claims 1 to 4 or the nitride template based on the metal substrate prepared by the method in any one of claims 5 to 8 is used as a substrate, and an n-AlGaN electron transmission layer, an AlGaN multiple quantum well structure with alternating high and low Al components and a p-AlGaN hole transmission layer are sequentially extended.
10. Use of a metal substrate based nitride template for epitaxy and device of GaAs or InP second generation semiconductor materials, characterized in that an epitaxial material or device is grown using the metal substrate based nitride template of any one of claims 1-4 or the metal substrate based nitride template prepared by the method of any one of claims 5-8 as a substrate;
the device is any one of LEDs, a photoelectric detector and an HEMT.
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