CN108364852A - A kind of high quality AlN and its preparation method and application - Google Patents
A kind of high quality AlN and its preparation method and application Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000012010 growth Effects 0.000 claims abstract description 19
- 229910052594 sapphire Inorganic materials 0.000 claims abstract description 13
- 239000010980 sapphire Substances 0.000 claims abstract description 13
- 208000012868 Overgrowth Diseases 0.000 claims abstract description 12
- 230000000737 periodic effect Effects 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000012546 transfer Methods 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000001020 plasma etching Methods 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000000407 epitaxy Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 238000003475 lamination Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001312 dry etching Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 3
- 230000008023 solidification Effects 0.000 claims description 3
- 235000012431 wafers Nutrition 0.000 claims description 3
- 229910004205 SiNX Inorganic materials 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 238000009616 inductively coupled plasma Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims 1
- 238000004544 sputter deposition Methods 0.000 abstract description 9
- 229910002704 AlGaN Inorganic materials 0.000 abstract description 3
- 230000003287 optical effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000000059 patterning Methods 0.000 description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MYDJEUINZIFHKK-UHFFFAOYSA-N 1,1,2-trichloroethane-1,2-diol Chemical compound OC(Cl)C(O)(Cl)Cl MYDJEUINZIFHKK-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 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
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
- H01L21/02367—Substrates
- H01L21/0237—Materials
- H01L21/0242—Crystalline insulating materials
-
- 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
- H01L21/02367—Substrates
- H01L21/02433—Crystal orientation
-
- 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
- H01L21/02513—Microstructure
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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
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
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- H—ELECTRICITY
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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
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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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
- H01L33/0066—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
- H01L33/007—Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
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Abstract
The present invention relates to a kind of AlN epitaxial films and its preparation method and application.The preparation method of the AlN epitaxial films, including：(1) AlN layers are sputtered on (0001) surface sapphire surface；(2) AlN with nanoscale concave surface hole periodic arrangement figure is made；(3) epitaxial lateral overgrowth polymerization process is completed；(4) continue epitaxial growth to target thickness, obtain AlN epitaxial films.The present invention obtains the AlN epitaxial films that surface atom grade is smooth, dislocation density is very low, to realizing that AlGaN bases deep ultraviolet high-performance optical electrical part and industry application are of great significance by graphically sputtering two core links of AlN templates and high temperature epitaxial lateral overgrowth.
Description
Technical field
The present invention relates to high quality AlN epitaxial films in a kind of (0001) surface sapphire substrate and preparation method thereof and answer
With belonging to III nitride semiconductor preparing technical field.
Background technology
High Al contents AlGaN and its low-dimensional quantum structure photoelectric functional material are to prepare solid-state deep ultraviolet (DUV) luminous two
The irreplaceable material system of pole pipe (LED) is passed in the field of environment protection such as sterilizing, water and air purification and large capacity information
The message areas such as defeated and storage have extensive use, are field and the production that current III- group-III nitride semiconductors most have development potentiality
One of industry.The realization of low-dislocation-density AlN is the key that high-performance AlGaN bases DUV-LED and basis.Due to quotient in the world at present
The AlN substrates of industry are expensive, size is small, and are difficult to obtain, ultraviolet band translucency (0001) surface sapphire lining well
Hetero-epitaxy AlN templates are current mainstream technology routes on bottom.However due to lattice mismatch and thermal mismatching, lead to this AlN
Often have in template and very high runs through dislocation density (109-1010cm-2).These can generally extend to device active region through dislocation
It is interior, seriously affect the performance boost of device.Thus break through the effective ways tool for preparing low-dislocation-density AlN on a sapphire substrate
There is particularly important meaning.
The common technology path for preparing AlN epitaxial films is mainly the following in the world at present：First, using technique
The method of parameter adjustment；Second is that using the method for clock；Third, using the method for multilayer alternating growth；Fourth, micro-, nanometer figure
The method etc. of shape substrate.Although these methods can promote the crystal quality of AlN epitaxial films to a certain extent, explore lower
The AlN of dislocation density, which also needs to further excavate, develops new technology.
Invention content
(1) technical problems to be solved
The technical problem to be solved by the present invention is to how AlN Dislocations density be reduced in (0001) surface sapphire substrate.
(2) technical solution
In order to solve the above-mentioned technical problem, the present invention in (0001) surface sapphire substrate by sputtering certain thickness first
AlN, then prepare graphical AlN templates, then realize that atomically flating, dislocation density are extremely low by epitaxial lateral overgrowth process
AlN epitaxial films.
The present invention is realized using following scheme.
A kind of preparation method of AlN epitaxial films, including：
(1) AlN layers are sputtered on (0001) surface sapphire surface；
(2) AlN with nanoscale concave surface hole periodic arrangement figure is made；
(3) epitaxial lateral overgrowth polymerization process is completed；
(4) continue epitaxial growth to target thickness, obtain AlN epitaxial films.
In step (1), the sputtering is with the sources high-purity Al and N2Plasma provides the sources Al and the sources N respectively, carries out magnetic
Control sputtering；The magnetron sputtering temperature is 300-900 DEG C, preferably 550-750 DEG C.AlN layers of the thickness range is 150-
500nm, preferably 250-350nm, further preferably 300nm.
In step (2), the array of the figure is the arrays such as two-dimensional rectangular, square, diamond shape, Hexagonal Close-packed, wherein
It is preferred with concave surface hole hexagonal periodic arrangement figure；The period control is at 0.5-2.5 microns, preferably 1-1.6 microns, further
Preferably 1.3-1.4 microns；The mesa width is 300-500nm.
In step (2), the nanoscale concave surface hole periodic arrangement figure can be used pattern transfer technology cooperation dry method and carve
Erosion is prepared；The pattern transfer technology is selected from nano impression；The dry etching method selects inductively coupled plasma
(ICP), reactive ion etching method.
Preferably, the AlN with concave surface hole periodic arrangement figure is comprised the following steps：
Step S1. deposits one layer of SiM on AlN layers, and applies a lamination print glue on the surfaces SiM, and dries；The SiM is
SiO2Or SiNx；
Step S2. is with silica gel mantle or IPS (Intermediate polymer stamp, intermediate polymer masterplate) conduct
The intermediate medium of pattern transfer by the pattern transfer to intermediate medium on silicon chip impression block, and toasts intermediate medium and makes it
Solidification；
Step S3. is imprinted the figure on intermediate medium under conditions of heating and uv-exposure using nano-imprinting apparatus
To coining glue；And make mask to imprint glue, the surfaces AlN are etched to using RIE equipment, figure is transferred to SiM from coining glue
On；
The residue glue on step S4. removal epitaxial wafers surface, and cleaning, drying, and mask is made with SiM, it is etched using RIE equipment
Figure is transferred to from SiM in AlN templates by AlN；
Step S5. cleans AlN templates.
Preferably, in step sl, deposition temperature range is 200-250 DEG C, and the thickness range of the SiM is 50-
200nm, preferably 60-80nm, further preferably 70nm；The thickness range of the coining glue is preferred for 300nm-1 μm, preferably
400-600nm, further preferably 500nm.
In step s3, the gas that SiM etchings use is oxygen (plasma) and boron chloride, range of flow 40-
60sccm, power ranging from 250-350W, etching frequency are 250Hz, and the time range of etching coining glue is 15-80 seconds,
It is 45-110 seconds to etch SiM time ranges.
In step s 4, it is the mixed solution of the concentrated sulfuric acid (98%) and hydrogen peroxide, mixed volume to remove the liquid that residue glue uses
Than for VH2SO4：VH2O2=3：1；Heating temperature is 100 DEG C；And the gas that AlN etchings use is chlorine, boron chloride and argon
Gas, the range of flow used is 30-75sccm, power ranging from 100-450W, and etching frequency is 250Hz.
In step s 5, the remaining silica of AlN template surfaces is removed with hydrofluoric acid, cleans AlN templates, removes metal
The rear drying such as ion, organic matter, the requirement that growth apparatus carries out extension preparation can be entered by reaching；Hydrofluoric acid also phosphoric acid generation
It replaces；It is respectively trichloro ethylene, alcohol, acetone and deionized water to clean the liquid that template uses.
In step (3), temperature is 1100-1500 DEG C in the epitaxial lateral overgrowth polymerization process, and growth pressure is low as possible, such as
50-100mbar, while also needing to configure the molar flow ratio of adjustment ammonia and metal organic source according to MOCVD.
In step (4), the epitaxial growth method is selected from metal-organic chemical vapor deposition equipment (MOCVD) or hydride
Vapour phase epitaxy (HVPE).
The present invention also provides one kind AlN epitaxial films made from the above method.
The present invention also provides above-mentioned AlN epitaxial films can not replace in preparation solid-state deep ultraviolet (DUV) light emitting diode (LED)
Application in the material system in generation.
(3) advantageous effect
The present invention is organically combined using the preparation of nano graph AlN templates with laterally overgrown, and position is effectively reduced
Dislocation density.On the one hand preparation process by sputtering AlN can effectively evade AlN epitaxial growths on a sapphire substrate institute necessary
The poor nucleating step of controllability, the stability and repeatability of AlN preparation processes can be improved；On the other hand pass through sputtering
The high orientation of AlN [0001] direction crystal grain may be implemented in the preparation process of AlN, helps to reduce in follow-up laterally overgrown
The proliferation for closing up position mistake when crystal column merges.In addition, the epitaxial lateral overgrowth for carrying out AlN based on nano patterning AlN templates can be with
It makes full use of the multi-panel growth competition mechanism of self-assembling formation in the template to carry out AlN growth course controls, makes full use of image force
To dislocation effect reduce AlN epitaxial films run through dislocation, to may finally obtain surfacing, through dislocation density it is low
High quality AlN epitaxial films.AlN method for manufacturing thin film provided by the invention have the characteristics that it is efficient, reproducible, be suitble to
It widelys popularize.
Description of the drawings
The flow chart of Fig. 1, AlN epitaxial films preparation method of the present invention.
Concave surface hole Hexagonal Close-packed graphic array schematic diagram on Fig. 2, impression block of the present invention；Circular white region
For the part etched down.
AlN laterally overgrowns Dislocations evolution mechanism figure on Fig. 3, nano patterning AlN templates；AlN Dislocations density
It is mainly determined by three dynamic process A-C, process A is that dislocation is upwardly extended by the traction of [0001] face image force on table top；It crosses
Journey B is the bending of dislocation caused by hole area scope of freedom image force；Process C, which is zone of convergency crystal orientation difference, causes dislocation to increase
Add.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Fig. 1 illustrates the AlN epitaxial film preparation methods provided by the invention that AlN templates are sputtered based on nano patterning
Core ideas, main there are three important steps：First, preparing certain thickness on (0001) surface sapphire using magnetically controlled sputter method
The AlN of degree；Second is that the nano patterning for preparing concave surface hole periodic arrangement sputters AlN templates；Third, passing through AlN epitaxial lateral overgrowths
Polymerization process effectively reduces in AlN and runs through dislocation；Specifically include following steps：
Step S1：Certain thickness AlN is prepared on (0001) surface sapphire using magnetically controlled sputter method.
AlN is prepared using magnetically controlled sputter method first in 2 inches of c- surface sapphire substrates, magnetron sputtering temperature is preferably
550-750 DEG C, general 200-300 nanometers of thickness control is preferred；
Step S2：It prepares concave surface hole periodic arrangement nano patterning and sputters AlN templates.It is as follows, preferably
Concave graphics array Hexagonal Close-packed array as shown in Figure 2 is preferred.
The first step deposits one layer of SiO in AlN templates2, and in SiO2Surface applies a lamination print glue, and dries；
Second step makes intermediate medium of the silica gel mantle as pattern transfer, and the pattern transfer on silicon chip is soft to silica gel
On film, and toasts mantle and make its solidification；
Third walks, and the figure on silica gel is stamped into coining glue under conditions of uv-exposure using nano-imprinting apparatus
On；And make mask to imprint glue, the surfaces AlN are etched to using RIE equipment, figure is transferred to SiO from coining glue2On；
4th step, the residue glue on removal epitaxial wafer surface, and cleaning, drying, and with SiO2Make mask, is etched using RIE equipment
Figure is transferred to from SiO2 in AlN templates by AlN；
5th step removes the remaining silica of AlN template surfaces, anti-corruption thorough cleaning substrate, removal gold with hydrofluoric acid
Belong to the rear drying such as ion, organic matter, the requirement that growth apparatus carries out extension preparation can be entered by reaching；
Step S3：High temperature epitaxy growing AIN is carried out in ready nano patterning sputtering AlN templates, is completed lateral
Extension polymerization process, high temperature epitaxy growing AIN layer temperature are 1200-1400 DEG C and are preferred that growth pressure is low as possible, such as 50-
100mbar need to use the molar flow ratio (V/III ratios) of the ammonia and metal organic source of optimization, specific to need to be matched according to MOCVD
Set adjustment.
Step S4：Continue the certain thickness AlN of high temperature epitaxy, reach target thickness to get.
S1, S2 and S3 step are fitted close by the present invention, and the technique of wherein step S1 and S2 is implemented in combination with to suitable thickness
It sputters AlN and carries out nano patterning preparation, by graphic model, figure period, the optimum choice of mesa width and step S3
The optimization of growth parameter(s) can be precisely controlled the polymerization process in growth course, effectively eliminate passing through on growth table top
Dislocation is worn, specific control mechanism is as shown in Figure 3.It, can by the Optimized Matching to substrate graphic parameter and epitaxial growth conditions
Effectively to realize that the image force high efficiency of the free crystal face in the epitaxial lateral overgrowth of control AlN by hole (void) bends position
Mistake, and then realize the efficient elimination to running through dislocation on table top.In addition, by optimization and adjustment to growthing process parameter, it is real
The cross growth speed optimized during existing AlN epitaxial lateral overgrowths, to effectively reduce the crystal orientation of neighboring die in AlN polymerization processes
Difference, and then few dislocation multiplication (process C).
In short, by the accurate matching of thickness, nano graph parameter and epitaxial growth parameters to sputtering AlN, can have
Effect accurately controls the polymerization process of AlN epitaxial lateral overgrowths, to realize the purpose for preparing high quality AlN epitaxial films.
Embodiment 1 (for preparing 4.5 microns of AlN templates)
S1：It is singly thrown in Sapphire Substrate in 2 inches of (0001) faces and 300nm thickness is sputtered using AlN thin film sputtering equipment
AlN。
S2:Concave graphics AlN templates are prepared, the specific steps are：
1) PECVD device is used to deposit the SiO of 70nm thickness in the AlN templates2, later again in the even lamination in its surface
Glue (GD-04) is printed, thickness 500nm, being put in toast 1 minute on 100 degrees Celsius of warm table makes adhesive curing.
2) by the pattern transfer on the period is 1 μm, Circularhole diameter is 550nm impression block (mesa dimensions 450nm)
Onto silica gel mantle, then use nano-imprinting apparatus (GD-N-03) under conditions of uv-exposure by the epipial figure of silica gel
It is impressed on coining glue.O2(plasma) flow 40sccm, boron chloride flow 40sccm, power 300W, etching frequency
Rate 250Hz, etching 50 seconds glue time of coining, 120 seconds etching silicon dioxide time.
3) use RIE-200iP equipment that figure is transferred to SiO from coining glue as mask to imprint glue2On, then with 200
DEG C H2SO4 and H2O2Mixed solution (VH2SO4：VH2O2=3：1) residue glue on surface is washed.
4) use RIE-200iP equipment with SiO2For mask by figure from SiO2It is transferred in AlN templates.Chlorine flowrate selects
For 50sccm, boron chloride flow 40sccm, argon flow amount 55sccm, power 300W, frequency 250Hz is etched, etches nitrogen
Change 25 minutes aluminium time.
5) with hydrofluoric acid solution by remaining SiO in AlN templates2Removal, obtains the AlN templates of nano patterning, and thorough
It is dried after bottom cleaning AlN templates.
S3：The AlN of nano patterning is put into MOCVD device (3 × 2 " Aixtron CCS FP-MOCVD) reative cell
Template is passed through H2, it is warming up at 1250 DEG C, stablizes 90 seconds, holding chamber pressure is 50mbar；It is passed through trimethyl aluminium
(TMAl) and ammonia and to keep its V/III molar ratio be 400 it, in 1250 DEG C of high temperature epitaxy growing AINs, completes each adjacent on table top
The complete polymerization of AlN crystal columns (thickness is about 1.5 microns).
It is constant to continue 1250 DEG C of high temperature, holding chamber pressure is 50mbar, and the V/III for adjusting ammonia and TMAl flows rubs
You continue to be passed through ammonia and TMAl, continue high temperature epitaxy growing AIN, until its thickness reaches 4.5 microns than being 200.
Compliance test result
1 gained AlN epitaxial films of embodiment are tested by detection method commonly used in the art：
(1) light microscope detects, 1 gained AlN epitaxial film flawlesses of embodiment；
(2) atomic force microscope detects, and 1 gained AlN epitaxial films of embodiment have atomically flating surface；
(3) X-ray diffractometer or transmission electron microscope detection, 1 gained AlN epitaxial films of embodiment have low dislocation close
Degree.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of AlN epitaxial films, which is characterized in that including：
(1) AlN layers are sputtered on (0001) surface sapphire surface；
(2) AlN with nanoscale concave surface hole periodic arrangement figure is made；
(3) epitaxial lateral overgrowth polymerization process is completed；
(4) continue epitaxial growth to target thickness, obtain AlN epitaxial films.
2. the preparation method of AlN epitaxial films according to claim 1, which is characterized in that in step (1), the magnetic control
Sputter temperature is 300-900 DEG C, preferably 550-750 DEG C；AlN layers of the thickness range is 150-500nm, preferably 250-
350nm。
3. the preparation method of AlN epitaxial films according to claim 1 or 2, which is characterized in that in step (2), the figure
The array of shape is two-dimensional rectangular, square, diamond shape, Hexagonal Close-packed array, preferably concave surface hole hexagonal periodic arrangement figure；
The period control is at 0.5-2.5 microns, preferably 1-1.6 microns, further preferably 1.3-1.4 microns；The mesa width
For 300-500nm.
4. according to the preparation method of any AlN epitaxial films of claim 1-3, which is characterized in that in step (2), institute
Nanoscale concave surface hole periodic arrangement figure is stated to be prepared using pattern transfer technology cooperation dry etching；The pattern transfer
Technology is selected from nano impression；The dry etching method selects inductively coupled plasma or reactive ion etching method.
5. the preparation method of AlN epitaxial films according to claim 4, which is characterized in that nanoscale concave surface hole
The AlN of periodic arrangement figure is comprised the following steps：
Step S1. deposits one layer of SiM on AlN layers, and applies a lamination print glue on the surfaces SiM, and dries；The SiM is SiO2Or
SiNx；
Step S2. is arrived the pattern transfer on silicon chip impression block using silica gel mantle or IPS as the intermediate medium of pattern transfer
On intermediate medium, and toasts intermediate medium and make its solidification；
Figure on intermediate medium is stamped into using nano-imprinting apparatus under conditions of heating and uv-exposure by step S3.
It prints on glue；And make mask to imprint glue, the surfaces AlN are etched to using RIE equipment, figure is transferred to from coining glue on SiM；
The residue glue on step S4. removal epitaxial wafers surface, and cleaning, drying, and mask is made with SiM, AlN is etched using RIE equipment,
Figure is transferred to from SiM in AlN templates；
Step S5. cleans AlN templates.
6. the preparation method of AlN epitaxial films according to claim 5, which is characterized in that in step sl, depositing temperature
Ranging from 200-250 DEG C, the thickness range of the SiM is 50-200nm, preferably 60-80nm；The thickness range of the coining glue
It is 300nm-1 μm, preferably 400-600nm.
7. the preparation method of AlN epitaxial films according to claim 5, which is characterized in that in step s3, SiM etchings
The gas used is oxygen ion body and boron chloride, range of flow 40-60sccm, power ranging from 250-350W,
Etching frequency is 250Hz.
8. according to the preparation method of any AlN epitaxial films of claim 1-7, which is characterized in that in step (3), institute
It is 1100-1500 DEG C to state temperature in epitaxial lateral overgrowth polymerization process；In step (4), it is organic that the epitaxial growth method is selected from metal
Object chemical vapor deposition or hydride gas-phase epitaxy.
9. AlN epitaxial films made from any preparation methods of claim 1-8.
10. application of the AlN epitaxial films described in claim 9 in preparing solid-state deep-UV light-emitting diode material system.
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| CN113897676A (en) * | 2021-09-26 | 2022-01-07 | 苏州紫灿科技有限公司 | Crack-free AlN epitaxial film and preparation method thereof |
| CN115341277A (en) * | 2022-10-17 | 2022-11-15 | 至芯半导体(杭州)有限公司 | AlN thin film and preparation method and application thereof |
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