CN106835269A - Laminated base plate for nitride epitaxial growth and forming method thereof - Google Patents
Laminated base plate for nitride epitaxial growth and forming method thereof Download PDFInfo
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- CN106835269A CN106835269A CN201710122936.5A CN201710122936A CN106835269A CN 106835269 A CN106835269 A CN 106835269A CN 201710122936 A CN201710122936 A CN 201710122936A CN 106835269 A CN106835269 A CN 106835269A
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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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
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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
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
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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
- C30B29/38—Nitrides
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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
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02439—Materials
- H01L21/02455—Group 13/15 materials
- H01L21/02458—Nitrides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/02436—Intermediate layers between substrates and deposited layers
- H01L21/02494—Structure
- H01L21/02496—Layer structure
- H01L21/02505—Layer structure consisting of more than two layers
- H01L21/02507—Alternating layers, e.g. superlattice
Abstract
A kind of laminated base plate for nitride epitaxial growth and forming method thereof, the laminated base plate includes：At least one set of stacked structure, the stacked structure includes nitridation hafnium layer and aln layer, and the nitridation hafnium layer and aln layer are stacked with；The laminated base plate has hexagonal crystallographic texture.The laminated base plate is adapted as the substrate of high growth temperature nitride epitaxial layer, forms high-quality nitride epitaxial layer.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly to a kind of laminated base plate for nitride epitaxial growth and its
Forming method.
Background technology
Used as third generation semiconductor, gallium nitride has excellent and unique electrical and optical properties, direct band gap such as wide, height
Thermal conductivity, big breakdown field strength, high temperature high voltage resistant, anticorrosive, radioresistance etc., are suitably applied in the environment of inclement condition.
Gallium nitride-based material can be used for ultraviolet/blue/green light emitting diode (LED), laser, photo-detector and high frequency, efficient, height
The fields such as pressure, high-power HEMT (HEMT).
Due to lacking homogeneity gallium nitride and aluminium chloride single crystalline substrate, the usual heteroepitaxial growth of gallium nitride is in sapphire, carbon
On the substrates such as SiClx, silicon, zinc oxide.Due to exist between gallium nitride and above-mentioned substrate lattice parameter and thermal coefficient of expansion not
Match somebody with somebody, cause the epitaxial layer of gallium nitride being epitaxially formed on a silicon substrate to be also easy to produce crackle and a large amount of dislocations or defect, crystal mass compared with
Difference, causes increasing for Carrier Leakage and non-radiative recombination center, reduces the internal quantum efficiency of device, have impact on device level
Raising.
Buffer intermediate layer technology is the key technology of dimensional electron extension, it directly affect epitaxial layer crystal mass and
Characterisitic parameter.At present, the buffer intermediate layer that GaN growth is used has low temperature nitride gallium layer, low temperature nitride aluminium lamination, high-temperature ammonolysis
Aluminium lamination, 3C- silicon carbide layers, zinc oxide film etc..Such as the epitaxy of gallium nitride of Sapphire Substrate, the method for generally using at present is low temperature
Growing nitride nucleating layer technology.Buffer intermediate layer makes gallium nitride carry out two-dimensional growth thereon, and stress is reduced, and suppresses extension
Defect is upwardly extended.Therefore, the crystal mass of material is improved.
But, the defect of the gallium nitride layer for being formed using high temperature growth processes at present is more, therefore, it is also desirable to provide new
Buffer intermediate layer, to improve the crystal mass of the nitride of high growth temperature formation.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of laminated base plate and its shape for nitride epitaxial growth
Into method, to provide a kind of buffer intermediate layer for being suitable to high growth temperature high-quality nitride layer.
In order to solve the above problems, the invention provides a kind of laminated base plate for nitride epitaxial growth, including：Extremely
Few one group of stacked structure, the stacked structure includes nitridation hafnium layer and aln layer, and the nitridation hafnium layer and aln layer are mutual
Stacking；The laminated base plate has hexagonal crystallographic texture.
Optionally, the thickness of the nitridation hafnium layer is 1nm~500nm；The thickness of the aln layer is 1nm~500nm.
Optionally, the quantity of the stacked structure is 1~500 group.
Optionally, the stacked structure is located at semiconductor substrate surface.
Optionally, the technique of the epitaxial growth includes metal organic chemical vapor deposition, molecular beam epitaxy or hydride
Vapour phase epitaxy.
Unresolved above mentioned problem, technical scheme also provides a kind of laminated base plate for nitride epitaxial growth
Forming method, including：At least one set of stacked structure is formed using vacuum deposition process, the stacked structure includes nitridation hafnium layer
And aln layer, the nitridation hafnium layer and aln layer are stacked with so that the laminated base plate of formation has hexagonal crystallographic texture.
Optionally, the vacuum deposition process includes ion beam depositing technique, magnetron sputtering technique or atomic layer epitaxy work
Skill.
Optionally, the thickness of the nitridation hafnium layer is 1nm~500nm；The thickness of the aln layer is 1nm~500nm.
Optionally, stacked structure described in 1~500 group is formed.
Optionally, the stacked structure is formed on a semiconductor substrate.
Laminated base plate of the invention includes the nitridation hafnium layer and aln layer of stacking, due to nitridation hafnium layer and the aluminium nitride
Misfit strain coordinative role between layer so that the laminated base plate has hexagonal crystallographic texture, with other metals such as gallium nitride
The lattice structure of nitride semi-conductor material is consistent, so as in the laminated base plate surface epitaxial growth nitride layer, Neng Gouyou
Effect alleviates the stress between Semiconductor substrate and epitaxial layer, it is to avoid the generation and the deterioration of crystal mass of crackle, so as to improve
The quality of the nitride layer.Also, the high-temperature stability of the nitridation hafnium layer and aln layer is good, high growth temperature work is being used
Skill can effectively stop that nitride epitaxial layer is sent out with the Semiconductor substrate when the laminated base plate surface forms nitride layer
Raw interfacial chemical reaction or the phenomenon of Interface composition counterdiffusion, with good impurity barrier effect.
The forming method of laminated base plate of the invention, sequentially forms the nitridation hafnium layer and aln layer that are stacked with as folded
Laminar substrate.The laminated base plate is adapted as the substrate of high growth temperature nitride epitaxial layer, can effectively alleviate Semiconductor substrate
Stress between nitride epitaxial layer, it is to avoid the generation and the deterioration of crystal mass of nitride epitaxial layer internal fissure, so that
Improve the quality of the nitride layer.
Brief description of the drawings
Fig. 1 is the structural representation of the laminated base plate for nitride epitaxial growth of the embodiment of the invention.
Specific embodiment
Below in conjunction with the accompanying drawings to the laminated base plate provided by the present invention for nitride epitaxial growth and forming method thereof
Specific embodiment elaborates.
Fig. 1 is refer to, is the structure of the laminated base plate for nitride epitaxial growth of the embodiment of the invention
Schematic diagram.
The laminated base plate 200 includes：At least one set of stacked structure, the stacked structure includes nitridation hafnium layer 201 and nitrogen
Change aluminium lamination 202, the nitridation hafnium layer 201 and aln layer 202 are stacked with；Also, the laminated base plate 200 has hexagonal crystal
Body structure.
In specific embodiment of the invention, the thickness of the nitridation hafnium layer 201 is 1nm~500nm；The aluminium nitride
The thickness of layer 202 is 1nm~500nm.The thickness of the nitridation hafnium layer 201 and aln layer 202 can be with identical, it is also possible to respectively
With different thickness.
There is a nitridation hafnium layer 201 and the aln layer positioned at nitridation hafnium layer 201 surface in the stacked structure
202.In specific embodiment of the invention, the quantity of the stacked structure is 1~500 group, i.e., described laminated base plate has 1
~500 layers of 201 layers of hafnium nitride, 202 layers of corresponding aluminium nitride with the identical number of plies.As shown in fig. 1, the laminated base plate
200 have three groups of stacked structures, i.e., described laminated base plate 200 includes three layers of nitridation 201, three layers of aln layer 202 of hafnium layer, and institute
State nitridation hafnium layer 201 and the stacked spaced apart of aln layer 202.
In this specific embodiment, the laminated base plate 200 is located at the surface of Semiconductor substrate 100, is partly led as described
Buffer intermediate layer between body substrate 100 and nitride layer to be formed.The Semiconductor substrate 100 includes silicon substrate, germanium
Substrate or germanium silicon substrate etc..With the surface directly contact of the Semiconductor substrate 100 can be nitridation hafnium layer 201, or
Aln layer 202.
In the laminated base plate 200, because the misfit strain between the nitridation hafnium layer 201 and aln layer 202 is coordinated
Effect so that the laminated base plate 200 has hexagonal crystallographic texture, with other metal nitride semiconductor's materials such as gallium nitride
Lattice structure is consistent, so as in the surface epitaxial growth nitride layer of the laminated base plate 200, can effectively alleviate Semiconductor substrate
Stress between 100 and epitaxial layer, it is to avoid the generation and the deterioration of crystal mass of crackle, so as to improve the nitride layer
Quality.Also, the high-temperature stability of the nitridation hafnium layer 201 and aln layer 202 is good, high temperature growth processes are being used described
When the surface of laminated base plate 200 forms nitride layer, can effectively stop that nitride epitaxial layer occurs with the Semiconductor substrate 100
Interfacial chemical reaction or the phenomenon of Interface composition counterdiffusion, with good impurity barrier effect.
Therefore, the laminated base plate 200 is suitable as the substrate of high temperature epitaxy growth nitride epitaxial layer.The extension life
Technique long is including metal organic chemical vapor deposition, molecular beam epitaxy or hydride gas-phase epitaxy etc..In the laminated base plate
The nitride layer formed on 200, such as gallium nitride layer, surfacing, number of dislocations is less, and crystal mass is high, can be used for light
The epitaxial growth of electricity and electronic structure material.
Specific embodiment of the invention also provides a kind of forming method of above-mentioned laminated base plate, including：It is heavy using vacuum
Product technique forms at least one set of stacked structure, and the stacked structure includes nitridation hafnium layer and aln layer, the nitridation hafnium layer and
Aln layer is stacked with so that the laminated base plate of formation has hexagonal crystallographic texture.
In the specific embodiment of the present invention, the stacked structure is formed on a semiconductor substrate.The vacuum
Depositing operation includes ion beam depositing technique, magnetron sputtering technique or atomic layer epitaxy process.Form the thickness of the nitridation hafnium layer
It is 1nm~500nm to spend；The thickness of the aln layer is 1nm~500nm, can successively in the semiconductor substrate surface shape
Into nitridation hafnium layer and aln layer, stacked structure described in 1~500 group is ultimately formed.
In one embodiment of the invention, using 8 inches of silicon substrate as Semiconductor substrate, crystal orientation is<111>, it is first
Silicon substrate is first carried out into the drying of organic solvent cleaning, hydrofluoric acid burn into deionized water rinsing and nitrogen successively, makes the silicon substrate
Thoroughly clean on surface.Then the clean silicon substrate is put into the deposit cavity of atomic layer epitaxy process, vacuum be 1 ×
10-4Pa, carries out atomic layer epitaxy deposition, and 250 DEG C~700 DEG C of silicon substrate temperature deposits one layer of nitridation in surface of silicon successively
Aluminium lamination, in one layer of nitridation hafnium layer of stacking, cyclic deposition successively forms laminated base plate.In cvd nitride aluminium lamination, hydrogen and nitrogen
It is carrier gas, flow is 10slm~80slm；N sources are NH3, flow is 20slm~80slm, such as 50slm；Silicon source is trimethyl
The gas with aluminium element such as aluminium, flow is 20slm~80slm；Growth pressure is 100mbar~800mbar.In cvd nitride
During hafnium layer, above-mentioned silicon source is replaced with into the gases containing hafnium element such as hafnium source, such as hafnium tetrachloride, flow is 20slm~80slm.
In one embodiment, the thickness of the aluminium nitride of formation is 2nm, and the thickness of hafnium nitride is 5nm, and 20 heaps are formed altogether
Layer aluminium nitride of stack structure, i.e., 20,20 layers of hafnium nitride, gross thickness is 140nm.
The laminated base plate that the above method is formed, because the misfit strain between the nitridation hafnium layer and aln layer is coordinated to make
With so that the laminated base plate has hexagonal crystallographic texture, is adapted as the substrate of high temperature epitaxy grown nitride layer.Can be by
The laminated base plate is placed in metal-organic chemical vapor deposition equipment stove, using mocvd process in institute
Laminated base plate surface epitaxial growth of gallium nitride epitaxial layer is stated, wherein, temperature is 100 DEG C~1110 DEG C, and N sources are ammonia, and flow is
50slm；Hydrogen and nitrogen are carrier gas, flow 10slm~80slm；Growth pressure is 100mbar~800mbar, and trimethyl gallium is made
It is gallium source.In other specific embodiments, the epitaxial growth technology of the nitride layer can also be Organometallic Chemistry gas
The high temperature epitaxial growth technologies such as phase deposition, molecular beam epitaxy or hydride gas-phase epitaxy.
The lattice knot of other metal nitride semiconductor's materials such as lattice structure and gallium nitride due to the laminated base plate
Structure is consistent, so as in the laminated base plate surface epitaxial growth nitride layer, can effectively alleviate Semiconductor substrate and epitaxial layer
Between stress, it is to avoid the generation and the deterioration of crystal mass of crackle, so as to improve the quality of the nitride layer.Also,
The high-temperature stability of the nitridation hafnium layer and aln layer is good, is formed on the laminated base plate surface using high temperature growth processes
During nitride layer, can effectively stop that nitride epitaxial layer occurs interfacial chemical reaction or Interface composition with the Semiconductor substrate
The phenomenon of counterdiffusion, with good impurity barrier effect.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, under the premise without departing from the principles of the invention, can also make some improvements and modifications, and these improvements and modifications also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of laminated base plate for nitride epitaxial growth, it is characterised in that including：
At least one set of stacked structure, the stacked structure includes nitridation hafnium layer and aln layer, the nitridation hafnium layer and aluminium nitride
Layer is stacked with；
The laminated base plate has hexagonal crystallographic texture.
2. laminated base plate according to claim 1, it is characterised in that the thickness of the nitridation hafnium layer is 1nm~500nm；
The thickness of the aln layer is 1nm~500nm.
3. laminated base plate according to claim 1, it is characterised in that the quantity of the stacked structure is 1~500 group.
4. laminated base plate according to claim 1, it is characterised in that the stacked structure is located at semiconductor substrate surface.
5. laminated base plate according to claim 1, it is characterised in that the technique of the epitaxial growth includes Organometallic
Learn vapour deposition, molecular beam epitaxy or hydride gas-phase epitaxy.
6. the forming method of a kind of laminated base plate for nitride epitaxial growth, it is characterised in that including：
At least one set of stacked structure is formed using vacuum deposition process, the stacked structure includes nitridation hafnium layer and aln layer,
The nitridation hafnium layer and aln layer are stacked with so that the laminated base plate of formation has hexagonal crystallographic texture.
7. the forming method of laminated base plate according to claim 6, it is characterised in that the vacuum deposition process include from
Beamlet depositing operation, magnetron sputtering technique or atomic layer epitaxy process.
8. the forming method of laminated base plate according to claim 6, it is characterised in that the thickness of the nitridation hafnium layer is
1nm~500nm；The thickness of the aln layer is 1nm~500nm.
9. the forming method of laminated base plate according to claim 6, it is characterised in that formed and knot is stacked described in 1~500 group
Structure.
10. the forming method of laminated base plate according to claim 6, it is characterised in that form institute on a semiconductor substrate
State stacked structure.
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| CN201710122936.5A CN106835269A (en) | 2017-03-03 | 2017-03-03 | Laminated base plate for nitride epitaxial growth and forming method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208337A (en) * | 2010-03-30 | 2011-10-05 | 杭州海鲸光电科技有限公司 | Silicon-base compound substrate and manufacturing method thereof |
| CN102598276A (en) * | 2009-09-03 | 2012-07-18 | 威世硅尼克斯 | Method of forming a semiconductor device |
| CN104576840A (en) * | 2013-10-15 | 2015-04-29 | 江苏积汇新能源科技有限公司 | Method for preparing gallium nitride LED (light-emitting diode) on silicon substrate |
-
2017
- 2017-03-03 CN CN201710122936.5A patent/CN106835269A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102598276A (en) * | 2009-09-03 | 2012-07-18 | 威世硅尼克斯 | Method of forming a semiconductor device |
| CN102208337A (en) * | 2010-03-30 | 2011-10-05 | 杭州海鲸光电科技有限公司 | Silicon-base compound substrate and manufacturing method thereof |
| CN104576840A (en) * | 2013-10-15 | 2015-04-29 | 江苏积汇新能源科技有限公司 | Method for preparing gallium nitride LED (light-emitting diode) on silicon substrate |
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Application publication date: 20170613 |