CN105543969B - A kind of growing method of improvement AlN film crystal quality - Google Patents
A kind of growing method of improvement AlN film crystal quality Download PDFInfo
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- CN105543969B CN105543969B CN201610044801.7A CN201610044801A CN105543969B CN 105543969 B CN105543969 B CN 105543969B CN 201610044801 A CN201610044801 A CN 201610044801A CN 105543969 B CN105543969 B CN 105543969B
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000013078 crystal Substances 0.000 title claims abstract description 22
- 230000006872 improvement Effects 0.000 title claims abstract description 6
- 230000012010 growth Effects 0.000 claims abstract description 48
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims abstract description 47
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000000407 epitaxy Methods 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 7
- 238000000137 annealing Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 57
- 229910052594 sapphire Inorganic materials 0.000 claims description 12
- 239000010980 sapphire Substances 0.000 claims description 12
- 238000010348 incorporation Methods 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- JOTBHEPHROWQDJ-UHFFFAOYSA-N methylgallium Chemical compound [Ga]C JOTBHEPHROWQDJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 32
- 229910021529 ammonia Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000011896 sensitive detection Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 229910018509 Al—N Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004630 atomic force microscopy Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
-
- 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
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A kind of growing method of improvement AlN film crystal quality, is related to the metal-organic chemical vapor deposition equipment MOCVD growing technologies field of III group-III nitride.The present invention uses two-step method growing AIN film, comprises the following steps：1）Cleaning baking substrate；2）Nitridation or pre- logical trimethyl aluminium；3）Low-temperature epitaxy AlN cushions；4）Heating annealing；5）High growth temperature AlN films；Above-mentioned steps 3）With step 5）In at least one step need to be passed through trimethyl gallium as surfactant.Compared with the existing technology, the AlN films prepared with the method for the present invention, have the characteristics that dislocation density is small, surface smoothness is good.
Description
Technical field
The present invention relates to the metal-organic chemical vapor deposition equipment MOCVD growing technologies field of III group-III nitride, is particularly
Improve the growing method of AlN film crystal quality.
Background technology
The deep ultraviolet DUV luminescent devices and sensitive detection parts of high Al contents AlGaN epitaxial films based on high quality can be wide
It is general to apply in the field such as disinfection, water and Food processing, biochemistry detection, information storage, radar detection and secure communication, market
Potentiality and application prospect are very huge.And the AlN substrates and template of high-crystal quality are to prepare above-mentioned high-performance deep-UV light-emitting
With the key foundation of sensitive detection parts.
The AlN single crystalline substrates of high quality are expensive at present, it is high to prepare difficulty.Therefore, in the prior art, international research person
Selection prepares the AlN films of high quality using metal-organic chemical vapor deposition equipment on a sapphire substrate, often selects two steps
Method or pulse law technology.
Al-N bond energys are 2.88eV (Ga-N bond energys are 1.93eV), are highest in group III-nitride, so Al atom keys
It is difficult desorption after conjunction, migrating required activation in growing surface can be very high.Therefore, during prepared by above-mentioned two-step method, the life of AlN extensions
Long to be mainly shown as three-dimensional island pattern, rough surface, island, which merges, easily produces dislocation and crystal boundary, causes dislocation density very big,
Seriously affect the performance of the ultraviolet electrical part of AlGaN bases.Further, since also there is higher heat mistake between AlN and Sapphire Substrate
Match somebody with somebody and lattice mismatch, exacerbate the deterioration of crystal quality.
The content of the invention
For above-mentioned the deficiencies in the prior art, the object of the present invention is to provide one kind to improve AlN film crystal matter
The growing method of amount.The AlN films prepared with this method, have the characteristics that dislocation density is small, surface smoothness is good.
In order to reach foregoing invention purpose, technical scheme is realized as follows：
A kind of growing method of improvement AlN film crystal quality, using two-step method growing AIN film, it is characterised in that bag
Include following steps：
1）Cleaning baking substrate；
2）Nitridation or pre- logical trimethyl aluminium；
3）Low-temperature epitaxy AlN cushions；
4）Heating annealing；
5）High growth temperature AlN films；
Above-mentioned steps 3）With step 5）In at least one step need to be passed through trimethyl gallium as surfactant.
In above-mentioned growing method, the step 1）Substrate use sapphire, silicon or carborundum in one kind.
In above-mentioned growing method, the step 2）Nitridation or pre- logical trimethyl aluminium process temperature be 500-1100 DEG C,
Chamber pressure is 20-200mbar, time 5-120s.
In above-mentioned growing method, the step 3）In AlN cushions epitaxial growth temperature be 500-1200 DEG C, reaction
Chamber pressure is 20-200mbar, and buffer layer thickness 5-100nm, V/III ratio is 100-10000.
In above-mentioned growing method, the step 5）In AlN thin film epitaxial growths temperature be 1000-1400 DEG C, reaction
Chamber pressure is 20-200mbar, and AlN film thicknesses are 1-5 μm, and V/III ratio is 10-1000.
In above-mentioned growing method, the trimethyl gallium that is passed through as surfactant, trimethyl gallium and trimethyl aluminium
Flow molar ratio is 0.1-1, and the Ga components in actual AlN layers of incorporation are 0.01-0.1.
In above-mentioned growing method, the step 5）In in high growth temperature AlN films, surfactant trimethyl gallium
The stage of being passed through is wherein certain part of flood or flood.
In above-mentioned growing method, the growing AIN method is metal-organic chemical vapor deposition equipment method.
The present invention compared with the existing technology has the following advantages that as a result of the above method：
The growing method of AlN epitaxial layers of the present invention uses two-step method, in low-temperature epitaxy AlN cushions or high growth temperature
Trimethyl gallium is passed through during AlN films as surfactant, or in low-temperature epitaxy AlN cushions and high growth temperature AlN films
When be all passed through trimethyl gallium as surfactant, can improve crystal quality and surface topography.Utilize surface migration ability phase
The transfer ability of III race's metallic atom of growing surface is improved to preferable Ga atoms, promotes the growth of step stream, improves surfacing
Degree so that relatively low growth temperature can be achieved with the two dimensional mode of AlN.In addition, the present invention AlN grow nucleation or into
When core merges, the nucleation size of incorporation Ga atom increase AlN crystal grain, can effectively reduce what is brought when growth island merges
Dislocation.
The present invention will be further described with reference to the accompanying drawings and detailed description.
Brief description of the drawings
Fig. 1 is the flow chart of growing method of the present invention；
Fig. 2 is to be passed through and be not passed through the XRD (102) for the AlN films that trimethyl gallium is grown in the embodiment of the present invention one
The rocking curve in face compares figure；
Fig. 3 is to be passed through and be not passed through three axis ω -2 θ of the AlN films that trimethyl gallium is grown in the embodiment of the present invention one
Scanning curve compares figure.
Embodiment
Referring to Fig. 1, the present invention improves the growing method of AlN film crystal quality, using two-step method growing AIN film, bag
Include following steps：
1）Cleaning baking substrate；Substrate uses one kind in sapphire, silicon or carborundum.
2）Nitridation or pre- logical trimethyl aluminium；Nitridation or pre- logical trimethyl aluminium process temperature are 500-1100 DEG C, react chamber pressure
Power is 20-200mbar, time 5-120s.
3）Using metal-organic chemical vapor deposition equipment method low-temperature epitaxy AlN cushions；AlN cushion epitaxial growth temperatures
For 500-1200 DEG C, chamber pressure 20-200mbar, buffer layer thickness 5-100nm, V/III ratio is 100-10000.
4）Heating annealing；
5）Using metal-organic chemical vapor deposition equipment method high growth temperature AlN films；AlN thin film epitaxial growth temperature is
1000-1400 DEG C, chamber pressure 20-200mbar, AlN film thickness are 1-5 μm, and V/III ratio is 10-1000.
Above-mentioned steps 3）With step 5）In at least one step need to be passed through trimethyl gallium as surfactant.Trimethyl
The flow molar ratio of gallium and trimethyl aluminium is 0.1-1, and the Ga components in actual AlN layers of incorporation are 0.01-0.1.In high growth temperature
During AlN films, surfactant trimethyl gallium is passed through wherein certain part that the stage is flood or flood.
Embodiment one：
According to following steps growing AIN film, trimethyl gallium is passed through in high growth temperature AlN films：
1）Chamber pressure is set as 150mbar, reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
Baking 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) trimethyl aluminium, trimethyl gallium and ammonia are passed through while, trimethyl aluminium and TMGa flow rate be respectively 25 and
The flow molar ratio of 300sccm, trimethyl gallium and trimethyl aluminium is that 1, V/III ratios are 100, keeps chamber pressure 50mbar,
Reaction chamber temperature is 1150 DEG C, high temperature epitaxy growing AIN, and thickness is 0.5 μm.Trimethyl gallium is then shut off, continues epitaxial growth
AlN, thickness are 1.5 μm.Growth gained AlN overall film thickness is 2 μm.
From figure 2 it can be seen that XRD (102) face halfwidth for being passed through the AlN films of trimethyl gallium growth is 650, hence it is evident that
Less than XRD (102) face halfwidth 980 for the AlN films for not being passed through trimethyl gallium growth.Illustrate to be passed through trimethyl gallium growth
AlN films can be obviously improved crystal quality.From figure 3, it can be seen that it is passed through three axis ω -2 of the AlN films of trimethyl gallium growth
It is low at AlN (002) peak compared with three axis ω -2 θ scanning curves of AlN films of the θ scanning curves with not being passed through trimethyl gallium growth
Substantially there are the relatively low small peak of a intensity, the corresponding AlN films for mixing a small amount of Ga in angle side, and Ga calculations are 0.05.
Embodiment two：
According to following steps growing AIN film, trimethyl gallium is passed through in high growth temperature AlN films：
1）Chamber pressure is set as 150mbar, reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) trimethyl aluminium, trimethyl gallium and ammonia are passed through while, trimethyl aluminium and TMGa flow rate be respectively 2.5 and
The flow molar ratio of 300sccm, trimethyl gallium and trimethyl aluminium is that 0.1, V/III ratios are 100, keeps chamber pressure
50mbar, reaction chamber temperature are 1150 DEG C, and high temperature epitaxy growing AIN, thickness is 0.3 μm.Trimethyl gallium is then shut off, is continued outer
Epitaxial growth AlN, thickness are 1.7 μm.Growth gained AlN overall film thickness is 2 μm.
Embodiment three：
According to following steps growing AIN film, trimethyl gallium is passed through in high growth temperature AlN films：
1）Chamber pressure is set as 150mbar, reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) trimethyl aluminium, trimethyl gallium and ammonia are passed through while, trimethyl aluminium and TMGa flow rate be respectively 12.5 and
The flow molar ratio of 300sccm, trimethyl gallium and trimethyl aluminium is that 0.5, V/III ratios are 100, keeps chamber pressure
50mbar, reaction chamber temperature are 1150 DEG C, and high temperature epitaxy growing AIN, thickness is 0.7 μm.Trimethyl gallium is then shut off, is continued outer
Epitaxial growth AlN, thickness are 1.3 μm.Growth gained AlN overall film thickness is 2 μm.
Example IV：
According to following steps growing AIN film, trimethyl gallium is passed through in high growth temperature AlN films：
1）Chamber pressure is set as 150mbar, reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) chamber pressure 50mbar is kept, reaction chamber temperature is 1150 DEG C, and V/III ratios are 100, high temperature epitaxy growth
AlN, thickness are 1 μm.Then trimethyl aluminium, trimethyl gallium and ammonia are passed through at the same time, and trimethyl aluminium is distinguished with TMGa flow rate
For 12.5 and 300sccm, the flow molar ratio of trimethyl gallium and trimethyl aluminium is 0.5, continues epitaxial growth AlN, thickness is 1 μ
m.Growth gained AlN overall film thickness is 2 μm.
Embodiment five：
According to following steps growing AIN film, trimethyl gallium is passed through in high growth temperature AlN films：
1）Chamber pressure is set as 150mbar, reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) trimethyl aluminium, trimethyl gallium and ammonia are passed through while, trimethyl aluminium and TMGa flow rate be respectively 12.5 and
The flow molar ratio of 300sccm, trimethyl gallium and trimethyl aluminium is that 0.5, V/III ratios are 100, keeps chamber pressure
50mbar, reaction chamber temperature are 1150 DEG C, and high temperature epitaxy growing AIN, thickness is 2 μm.
Embodiment six：
According to following steps growing AIN film, trimethyl gallium is passed through in low-temperature epitaxy AlN cushions：
1) chamber pressure is set as 150mbar, and reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
It is passed through trimethyl aluminium, trimethyl gallium and ammonia at the same time, TMGa flow rate is respectively 10sccm, trimethyl gallium and trimethyl aluminium
Flow molar ratio is that 0.1, V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) while trimethyl aluminium and ammonia are passed through, V/III molar ratios are 200, keep chamber pressure 50mbar, reaction
Room temperature is 1150 DEG C, high temperature epitaxy growing AIN, and thickness is 2 μm.
Embodiment seven：
According to following steps growing AIN film, three are all passed through in low-temperature epitaxy AlN cushions and high growth temperature AlN films
Methyl gallium：
1) chamber pressure is set as 150mbar, and reaction chamber temperature is 1100 DEG C, by Sapphire Substrate in atmosphere of hydrogen
In, toast 10 minutes.
2) 950 DEG C are cooled to, pre- logical trimethyl aluminium 10s.
3) chamber pressure is down to 100mbar, is warming up to 1000 DEG C of growing AIN cushions, growth thickness 20nm,
It is passed through trimethyl aluminium, trimethyl gallium and ammonia at the same time, TMGa flow rate is respectively 10sccm, trimethyl gallium and trimethyl aluminium
Flow molar ratio is that 0.1, V/III ratios are 1000.
4) chamber pressure is down to 50mbar, stops logical trimethyl aluminium, continue to be passed through ammonia, with 400 second time temperature
Degree rises to 1150 DEG C, stablizes 60s.
5) trimethyl aluminium, trimethyl gallium and ammonia are passed through while, trimethyl aluminium and TMGa flow rate be respectively 25 and
The flow molar ratio of 300sccm, trimethyl gallium and trimethyl aluminium is that 1, V/III ratios are 100, keeps chamber pressure 50mbar,
Reaction chamber temperature is 1150 DEG C, high temperature epitaxy growing AIN, and thickness is 0.5 μm.Trimethyl gallium is then shut off, continues epitaxial growth
AlN, thickness are 1.5 μm.Growth gained AlN overall film thickness is 2 μm.
The crystal quality of AlN epitaxial films is characterized using X-ray diffraction rocking curve halfwidth, utilizes atomic force microscopy
Mirror characterizes the surface roughness of AlN epitaxial films.It turns out that the AlN extensions of growing method growth using the present invention are thin
Film is compared with the sample that usual conditions are grown, and crystal quality significantly improves, and surface roughness is obviously reduced.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations.Although with reference to the foregoing embodiments
The present invention is described in detail, those of ordinary skill in the art still can be to the skill described in foregoing embodiments
Art scheme is modified, or carries out equivalent substitution to which part technical characteristic；It is all belong to shown according to the technical program
And the modification or replacement being clear to, the essence of appropriate technical solution is departed from various embodiments of the present invention technical solution, belong to
In protection scope of the present invention.
Claims (7)
- A kind of 1. growing method of improvement AlN film crystal quality, using two-step method growing AIN film, it is characterised in that including Following steps：1）Cleaning baking substrate；2）Nitridation or pre- logical trimethyl aluminium；3）Low-temperature epitaxy AlN cushions；4）Heating annealing；5）High growth temperature AlN films；Above-mentioned steps 3）With step 5）In at least one step need to be passed through trimethyl gallium as surfactant, it is described to be passed through three For methyl gallium as surfactant, the flow molar ratio of trimethyl gallium and trimethyl aluminium is 0.1-1, in actual AlN layers of incorporation Ga components are 0.01-0.1.
- 2. improve the growing method of AlN film crystal quality according to claim 1, it is characterised in that the step 1）'s Substrate uses one kind in sapphire, silicon or carborundum.
- 3. the growing method of improvement AlN film crystal quality according to claim 1 or claim 2, it is characterised in that the step 2） Nitridation or pre- logical trimethyl aluminium process temperature be 500-1100 DEG C, chamber pressure 20-200mbar, time 5-120s.
- 4. improve the growing method of AlN film crystal quality according to claim 3, it is characterised in that the step 3）In AlN cushions epitaxial growth temperature be 500-1200 DEG C, chamber pressure 20-200mbar, buffer layer thickness 5- 100nm, V/III ratio is 100-10000.
- 5. improve the growing method of AlN film crystal quality according to claim 4, it is characterised in that the step 5）In AlN thin film epitaxial growths temperature be 1000-1400 DEG C, chamber pressure 20-200mbar, AlN film thickness be 1-5 μm, V/III ratio is 10-1000.
- 6. improve the growing method of AlN film crystal quality according to claim 5, it is characterised in that the step 5）In In high growth temperature AlN films, surfactant trimethyl gallium is passed through wherein certain part that the stage is flood or flood.
- 7. improve the growing method of AlN film crystal quality according to claim 6, it is characterised in that the growing AIN side Method is metal-organic chemical vapor deposition equipment method.
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| CN106128937B (en) * | 2016-07-12 | 2019-03-29 | 河源市众拓光电科技有限公司 | A kind of high quality AlN film of epitaxial growth on a si substrate and preparation method thereof |
| CN106252211A (en) * | 2016-09-21 | 2016-12-21 | 中山大学 | A kind of preparation method of AlN epitaxial layer |
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| CN109994377A (en) * | 2019-03-27 | 2019-07-09 | 北京大学 | A kind of high-quality AlN epitaxial thin film and its preparation method and application |
| CN112725896B (en) * | 2019-10-28 | 2022-04-22 | 宁波安芯美半导体有限公司 | Preparation method of aluminum nitride single crystal film, aluminum nitride single crystal film and light-emitting diode |
| CN111341889B (en) * | 2020-03-07 | 2021-04-13 | 孙蕾蕾 | Method for forming semiconductor lighting epitaxial structure |
| CN116145251A (en) * | 2023-01-17 | 2023-05-23 | 北京中博芯半导体科技有限公司 | AlN thin film preparation method and semiconductor element |
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