CN106328772B - A kind of preparation method of high quality nitride epitaxial piece - Google Patents
A kind of preparation method of high quality nitride epitaxial piece Download PDFInfo
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- CN106328772B CN106328772B CN201610739620.6A CN201610739620A CN106328772B CN 106328772 B CN106328772 B CN 106328772B CN 201610739620 A CN201610739620 A CN 201610739620A CN 106328772 B CN106328772 B CN 106328772B
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 20
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical group NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 claims description 4
- 229940067157 phenylhydrazine Drugs 0.000 claims description 4
- 239000013078 crystal Substances 0.000 abstract description 6
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 26
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- -1 AlN nitride Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
- H01L33/0062—Processes for devices with an active region comprising only III-V compounds
- H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/12—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a stress relaxation structure, e.g. buffer layer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
A kind of preparation method of high quality nitride epitaxial piece, is related to a kind of growing technology field of LED epitaxial slice.The present invention is successively epitaxially-formed nitride buffer layer and nitride layer on substrate, in extension growing nitride buffer layer, it is passed through V race N source predecessor and III group metallo-organic compound, the V race N source predecessor is the organic nitrogen source and NH by low decomposition temperature3The mixture of composition.The present invention passes through while using the organic nitrogen source and NH of low decomposition temperature3For the source N needed for epitaxial growth, both allotments ratio improves the growth of nitride buffer layer under the conditions of the V/III of optimization ratio, obtains negligible amounts, the biggish crystal seed of crystal grain, the sufficient active source N is obtained, to improve the quality of nitride epitaxial piece.
Description
Technical field
The present invention relates to a kind of growing technology fields of LED epitaxial slice.
Background technique
Group III-nitride (InN, GaN and AlN) and its relevant multi-element compounds are as very important broad-band gap half
Conductor material, plays an important role in the semiconductor device, especially for photoelectric device.
LED growth technology is caused due to substrate used and extension interlayer lattice constant and the difference of thermal expansion coefficient
There are more dislocation defects in Material growth, device performance is influenced, report mainly passes through graphical substrate technology or substrate at present
The nitride buffer layer technology of upper growing AIN or GaN obtains negligible amounts, the biggish nitride seed of crystal grain in nucleating layer, changes
The crystal quality of kind GaN, AlGaN and InGaN epitaxial nitride layer.How further to improve nitride epitaxial layer crystal quality according to
Old is service workers' research emphasis.
Summary of the invention
Object of the present invention is to propose a kind of preparation method of high quality nitride epitaxial piece.
The present invention is successively epitaxially-formed nitride buffer layer and nitride layer on substrate, in extension growing nitride
When buffer layer, it is passed through V race N source predecessor and III group metallo-organic compound；The invention has the characteristics that the V race N source forerunner
Object is the organic nitrogen source and NH by low decomposition temperature3The mixture of composition.
The present invention passes through while using the organic nitrogen source and NH of low decomposition temperature3For the source N needed for epitaxial growth, allotment two
Person's ratio improves the growth of nitride buffer layer under the conditions of the V/III of optimization ratio, obtains negligible amounts, the biggish crystalline substance of crystal grain
Kind, the sufficient active source N is obtained, to improve the quality of nitride epitaxial piece.
In addition, the V race N source predecessor and III group Organometallic close when the nitride buffer layer described in epitaxial growth
The mixed volume ratio of object is 50~200: 1, the organic nitrogen source and NH of low decomposition temperature in the predecessor of the source V race N3Mixture
Product is than being 0.01~1: 1.
In the range of V race N source predecessor and the metal-organic mixed volume ratio of III group are 50~200: 1, than
It is easier to the partial pressure of each race's gas source when regulation growth, and then growing environment is realized, realizes AlN nitride buffer layer two dimension
The switching of planar growth and three-dimensional structure growth.
And in the predecessor of the source V race N low decomposition temperature organic nitrogen source and NH3Model of the mixed volume ratio 0.01~1: 1
When enclosing interior, the organic nitrogen source of low decomposition temperature primarily serves the allotment effect of the source N supply, because its decomposition temperature is relatively low, in temperature
It can reach 50% or more decomposition efficiency under conditions of being 400~600 DEG C, therefore when low-temperature epitaxy nitride buffer layer, regulate and control low
The supply ratio of warm organic nitrogen source, i.e., the delivery rate of controllable N, and NH3Reach higher decomposition efficiency, decomposition temperature
It needs at 800 DEG C or more, therefore NH when low-temperature nitride buffer growth3It primarily serves and maintains V race N source predecessor and III group gold
Belong to the effect of the flow proportional of organic compound.
Preferably, the organic nitrogen source of low decomposition temperature of the present invention is uns-dimethylhydrazine or phenylhydrazine.
Using low decomposition temperature organic nitrogen source uns-dimethylhydrazine or phenylhydrazine and NH3Mixing is used as the source N predecessor, can basis
Growth morphology needs to deploy organic nitrogen source and the ratio of NH3, organic by increasing low decomposition temperature when needing planar growth
The ratio of nitrogen source promotes more sources N predecessor to separate at a low growth temperature, and the source N is made to be easier to adsorb on substrate, in shape
When at nitride film, III group metal is easy to be formed two-dimensional surface growth by the distribution of N atom, increases nitride film
Nucleation probability, and then obtain more plane wider spaces.When needing three dimensional growth, by reducing low decomposition temperature organic nitrogen source
Ratio, so that the source N is in insufficient state, at a low growth temperature, itself mobility is relatively low in conjunction with III group metallic atom
The characteristics of, easily occur to reunite with growing to form three-dimensional structure.Nitride buffer layer grows through two-dimensional surface growth and three-dimensional structure
The switching of growth regulates and controls, and promotes stress release when subsequent nitride growth.
In addition, the epitaxial growth temperature of the nitride buffer layer is 400~600 DEG C, growth atmosphere H2。
Nitride buffer layer growth temperature is controlled at 400~600 DEG C, is mostly derived from the low temperature organic nitrogen source in this point
It can reach 50% or more decomposition efficiency at a temperature of solution.The decomposition efficiency favorably provides sufficient active N, promotes N in substrate
Absorption, and then promote the two-dimensional surface growth of nitride buffer layer.In addition because mobility is inclined at low temperature for III group metallic atom
It is low, therefore the control of nitride buffer layer growth temperature is grown at 400~600 DEG C, and the life of three-dimensional structure is favorably realized by the feature
Length, the allotment of the source growth temperature combination both the above N predecessor ratio and V race N source predecessor and III group metallic compound
The allotment of flow proportional realizes that the growth of nitride buffer layer two-dimensional surface and the switching of three-dimensional structure growth regulate and control.
The growth atmosphere of nitride buffer layer is H2, utilize H2Heat-conductive characteristic with higher can preferably transmit input
Heat, keep growing environment temperature to be uniformly distributed, and then promote the homogeneity of Material growth.
Specific embodiment
Embodiment 1:
The present invention provides a kind of GaN base epitaxial growth method, suitable for preparing high brightness GaN-based LED epitaxial wafer, this method
Steps are as follows:
1, grow one layer of nitride buffer layer on a sapphire substrate: 400~600 DEG C of growth temperature, pressure is
65000Pa, the growth source N are uns-dimethylhydrazine and NH3, uns-dimethylhydrazine and NH3Mixed volume ratio be 0.01~1: 1, and be passed through III
Race's metallo-organic compound.
The source V race N mixed precursor (i.e. uns-dimethylhydrazine and NH3) with the metal-organic mixed volume ratio of III group be
50~200: 1.
Atmosphere is H when growth2, and the source N and III group source metal are passed through using the above mixing ratio, form nitride buffer layer
With a thickness of 30nm.
2, raising temperature is to 1000~1250 DEG C, the grown nitride layer on nitride buffer layer: pressure 40000Pa,
Growing the source N is uns-dimethylhydrazine and NH3Mixture, uns-dimethylhydrazine and NH3Mixed volume ratio be 0.01~1: 1, while being passed through III
Race's metallo-organic compound.
The source V race N mixed precursor (i.e. uns-dimethylhydrazine and NH3) with the metal-organic mixed volume ratio of III group be
50~200: 1.
Atmosphere is H when growth2, and the source N and III group source metal are passed through using the above mixing ratio, form nitride buffer layer
With a thickness of 3 μm.
Embodiment 2:
The present embodiment and the difference of embodiment one are only that: uns-dimethylhydrazine is changed to phenylhydrazine.
Same to go out to be formed epitaxially one after the other nitride buffer layer and nitride layer on a sapphire substrate, properties of product are suitable
With upper example product.
Claims (2)
1. a kind of preparation method of high quality nitride epitaxial piece, be successively epitaxially-formed on substrate nitride buffer layer and
Nitride layer is passed through V race N source predecessor and III group metallo-organic compound in extension growing nitride buffer layer；The V
Race N source predecessor is the organic nitrogen source and NH by low decomposition temperature3The mixture of composition；It is characterized by: the low decomposition temperature
The organic nitrogen source of degree is phenylhydrazine；The epitaxial growth temperature of the nitride buffer layer is 400~600 DEG C, and growth atmosphere is
H2。
2. preparation method according to claim 1, it is characterised in that: when the nitride buffer layer described in epitaxial growth, institute
It states V race N source predecessor and the metal-organic mixed volume ratio of III group is 50~200: 1, in the predecessor of the source V race N
The organic nitrogen source and NH of low decomposition temperature3Mixed volume ratio be 0.01~1: 1.
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| CN102903615B (en) * | 2012-10-18 | 2018-02-06 | 中山大学 | P-type GaN and AlGaN semiconductor material a kind of preparation method |
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