CN118613133A - Method for growing high-quality Al (Sc) N thick film on Si substrate - Google Patents
Method for growing high-quality Al (Sc) N thick film on Si substrate Download PDFInfo
- Publication number
- CN118613133A CN118613133A CN202410666902.2A CN202410666902A CN118613133A CN 118613133 A CN118613133 A CN 118613133A CN 202410666902 A CN202410666902 A CN 202410666902A CN 118613133 A CN118613133 A CN 118613133A
- Authority
- CN
- China
- Prior art keywords
- substrate
- thick film
- quality
- aln
- single crystal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000137 annealing Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 238000005240 physical vapour deposition Methods 0.000 claims abstract description 8
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000009832 plasma treatment Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 239000007943 implant Substances 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 14
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 16
- 238000005530 etching Methods 0.000 description 5
- 229910052594 sapphire Inorganic materials 0.000 description 3
- 239000010980 sapphire Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000000407 epitaxy Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000542 Sc alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001534 heteroepitaxy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Abstract
The invention discloses a method for growing a high-quality Al (Sc) N thick film on a Si substrate, and belongs to the technical field of semiconductors. The method comprises the steps of firstly using MOCVD or MBE to grow a high-quality AlN single crystal layer on a Si substrate, then forming alpha-alumina on the surface layer of MOCVD/MBE AlN by means of oxygen plasma and thermal annealing, and finally depositing an Al (Sc) N thick film by PVD. The invention fully utilizes the characteristic that AlN and alpha-alumina which are easy to peel on a Si substrate can grow with excellent crystal quality, and grows Al (Sc) N material with better crystal quality and no cracking, which can be used for filter devices.
Description
Technical Field
The invention belongs to the technical field of semiconductors, and particularly relates to a method for growing a high-quality Al (Sc) N thick film on a Si substrate.
Background
With the continuous improvement of wireless terminal communication technology, the requirements for the frequency band of the filter are also continuously increasing. To meet these requirements, filter devices are continuously developed, and the requirements for materials are continuously changed from surface acoustic wave filters (SAW) to bulk acoustic wave filters (BAW). In order to realize a filter device with high frequency band, high electromechanical coupling coefficient, high Q value and high bandwidth, an Al (Sc) N material gradually becomes one of main materials of the filter device due to the characteristics of high sound velocity, high piezoelectric constant and high Q value.
The half-width of the (002) rocking curve of the Al (Sc) N material influences the Q value to a great extent, is more obvious in a high frequency band, and is more urgent for the improvement of the half-width of the (002) rocking curve of the Al (Sc) N material in the future in the age of 5G/6G Hz.
Si is used as a material for mature application in an integrated circuit, has the characteristic of easy stripping, and the material grown on the Si substrate is suitable for the processing requirement of a filter. Because of the large lattice mismatch and thermal mismatch between the Al (Sc) N grown on Si substrates and the substrates, it is difficult to directly grow high quality Al (Sc) N with a thickness greater than 300nm on Si substrates using MOCVD (metal organic chemical vapor deposition) and MBE (molecular formula epitaxy) growth methods. Although internationally a high quality thick film (Shen,J.et al.High quality AlN film grown on a nano-concave-circle patterned Si substrate with an AlN seed layer.Applied Physics Letters 117(2020).), is grown by using patterned substrates, the voids caused by the patterned substrates make it impossible to meet the processing requirements of BAW devices. Although the sapphire substrate is not easy to be stripped, the ultra-narrow half-width Al (Sc) N thick film material is easily realized on the sapphire substrate by a PVD (physical vapor deposition) method (Shojiki,K.,Uesugi,K.,Xiao,S.&Miyake,H.Polarity control of sputter-deposited AlN with high-temperature face-to-face annealing.Materials Science in Semiconductor Processing 166(2023).).
Disclosure of Invention
In order to solve the above problems in the prior art, an object of the present invention is to provide a method for growing high quality Al (Sc) N thick films on Si substrates.
In order to achieve the purpose of growing a high-quality Al (Sc) N thick film on a Si substrate, the invention firstly uses an MOCVD or MBE method to generate an AlN single crystal layer with good crystal quality, then carries out oxygen plasma treatment on the outermost surface of the aluminum nitride single crystal layer, and because O atoms do not etch AlN under low energy, the O atoms can be injected into an AlN thin film range with the surface within 10 nm; thermally annealing the AlN film on Si to form alpha-alumina on the outermost layer of the AlN film; the material Al (Sc) N applied to the filter device is then deposited by virtue of the easy growth of AlN single crystals on the sapphire substrate. The alpha-alumina only appears on the outermost layer of the MOCVD/MBE AlN single crystal film, so that the thickness is extremely small, the intermediate layer does not influence the manufacturing process for the BAW device, and finally, the high-quality Al (Sc) N thick film which can be used for the manufacturing process of the BAW device is grown on the Si substrate.
The invention is realized by the following technical scheme:
A method of growing a high quality Al (Sc) N thick film on a Si substrate comprising the steps of:
step 1, growing a high-quality AlN single crystal buffer layer on a Si substrate by using MOCVD or MBE;
step 2, forming alpha-alumina on the surface layer of the AlN single crystal buffer layer through oxygen plasma treatment and thermal annealing;
and 3, depositing an Al (Sc) N thick film on the alpha-alumina surface layer by adopting PVD.
In the above step 1, the Si substrate used may be a Si (100) substrate or a Si (111) substrate. The size of the Si substrate is not limited.
The thickness of the MOCVD or MBE grown AlN single crystal buffer layer is preferably 50-200nm.
In the step 2, the oxygen plasma may be generated in various ways, for example, the ion implanter or the ICP etcher may be used to bombard or implant low-energy oxygen plasma on the surface of the AlN single crystal buffer layer.
Preferably, oxygen plasma treatment is carried out in an ICP etching machine, the power of ICP etching is 50-300W, the bias power is 15-200W, the atmosphere is oxygen, and other gases such as nitrogen, argon and the like can be simultaneously introduced as an aid.
The temperature of the thermal annealing is 900-1400 ℃, nitrogen or other inert gases are selected as the atmosphere during the thermal annealing, the oxygen content is lower than 10%, and the time of the thermal annealing can be 1min-20h.
In the step 3, the deposited material comprises AlN and Al 1-xScx N (wherein x is more than or equal to 0 and less than or equal to 0.5).
Preferably, the thickness of the Al (Sc) N thick film is 200-20000nm.
Further, oxygen may be optionally introduced during deposition of the Al (Sc) N material to improve the stress state.
Further, PVD may be performed with a secondary anneal after deposition of Al (Sc) N at a temperature of 900-1400 ℃.
The invention has the beneficial effects that:
The invention provides a method for growing high quality Al (Sc) N thick films on Si substrates, firstly using MOCVD or MBE to grow high quality AlN single crystal layers, then forming alpha-alumina on the surface layers of MOCVD/MBE AlN by means of oxygen plasma and thermal annealing, and finally depositing Al (Sc) N on the treated surfaces. The invention fully utilizes the characteristic that AlN and alpha-alumina which are easy to peel on a Si substrate can grow with excellent crystal quality, and grows Al (Sc) N material with better crystal quality and no cracking, which can be used for filter devices.
Drawings
FIG. 1 is a flow chart of a method of the present invention for growing high quality Al (Sc) N thick films on Si substrates.
Fig. 2 is a schematic structural diagram of a high quality Al (Sc) N epitaxy grown on a Si substrate according to an embodiment of the invention, wherein: 1-Si substrate, 2-MOCVD/MBE AlN buffer layer, 3-oxygen plasma treated surface, 4-PVD Al (Sc) N.
Detailed Description
The technical scheme of the present invention will be described in further detail by way of examples with reference to the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Example 1
FIG. 2 is a schematic structural diagram of a single crystal III-nitride hetero-epitaxy prepared according to an embodiment of the present invention, and the growth method includes the steps of
Step 1, growth of a monocrystalline AlN buffer layer was performed on a 4 inch Si (111) substrate using MOCVD.
The method specifically comprises the following steps: firstly, 10sccm TMAL 60s is introduced, then 30sccm NH 3 is introduced, and the growth is carried out for 600s at 1100 ℃; then TMAL flow was set at 20sccm, NH 3 flow was set at 100sccm, pressure was set at 100mbar and growth at 1300℃for 2000s was performed.
And 2, forming alpha-alumina on the surface layer of the AlN buffer layer by means of oxygen plasma and thermal annealing.
The method specifically comprises the following steps: an ICP etching machine is selected to generate oxygen plasma, a sample is placed in the ICP etching machine, the power of ICP etching is 100W, the bias power is 15W, 20sccm of oxygen is introduced, and the treatment time is 30s; and then annealed at 1200 c for 1h under nitrogen atmosphere.
And 3, depositing Al 0.8Sc0.2 N on the surface of the sample treated in the step 2.
The method specifically comprises the following steps: and performing magnetron sputtering by selecting an Al/Sc alloy target, wherein the PVD power is set to 1800W, the nitrogen flow is 20sccm, the argon flow is 140sccm, the deposition time is 4000s, and the thickness of an epitaxial layer is 600nm.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (10)
1. A method of growing a high quality Al (Sc) N thick film on a Si substrate comprising the steps of:
1) Growing an AlN single crystal buffer layer on the Si substrate by using MOCVD or MBE;
2) Forming alpha-alumina on the surface layer of the AlN single crystal buffer layer through oxygen plasma treatment and thermal annealing;
3) A thick film of Al (Sc) N was deposited on the α -alumina surface layer using PVD.
2. The method of claim 1, wherein the Si substrate is a Si (100) substrate or a Si (111) substrate.
3. The method of claim 1, wherein the AlN single crystal buffer layer in step 1) has a thickness of 50-200nm.
4. The method of claim 1, wherein step 2) uses an ion implanter or an ICP etcher to bombard or implant oxygen plasma on the AlN single crystal buffer layer surface.
5. The method of claim 4, wherein step 2) is performed by oxygen plasma treatment in an ICP etcher with a power of 50-300W, a bias power of 15-200W, an atmosphere of oxygen, or introducing nitrogen or argon as an assist gas while introducing oxygen.
6. The method of claim 1, wherein step 2) is a thermal anneal in an inert atmosphere at a temperature of 900 ℃ to 1400 ℃.
7. The method of claim 1 wherein the composition of said Al (Sc) N thick film in step 3) is Al 1- xScx N, wherein 0.ltoreq.x.ltoreq.0.5.
8. The method according to claim 1, wherein the thickness of the Al (Sc) N thick film in step 3) is 200-20000nm.
9. The method according to claim 1, characterized in that step 3) PVD deposition of Al (Sc) N is followed by a secondary annealing at a temperature of 900-1400 ℃.
10. Use of a thick film of Al (Sc) N prepared by the method of any one of claims 1 to 9 in a filter device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410666902.2A CN118613133A (en) | 2024-05-28 | 2024-05-28 | Method for growing high-quality Al (Sc) N thick film on Si substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410666902.2A CN118613133A (en) | 2024-05-28 | 2024-05-28 | Method for growing high-quality Al (Sc) N thick film on Si substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118613133A true CN118613133A (en) | 2024-09-06 |
Family
ID=92566375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410666902.2A Pending CN118613133A (en) | 2024-05-28 | 2024-05-28 | Method for growing high-quality Al (Sc) N thick film on Si substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118613133A (en) |
-
2024
- 2024-05-28 CN CN202410666902.2A patent/CN118613133A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101556054B1 (en) | SEMICONDUCTOR WAFER WITH A LAYER OF AlzGa1-zN AND PROCESS FOR PRODUCING IT | |
| JPH076950A (en) | Manufacture of structural parts for electron, lightning and optical constituent | |
| JP2008531458A (en) | Single-step high-temperature nucleation method for lattice-mismatched substrates | |
| CN112687526B (en) | Preparation method of nitride semiconductor material and annealing treatment method thereof | |
| CN105190842A (en) | Film formation method, method for manufacturing semiconductor light-emitting element, semiconductor light-emitting element, and lighting apparatus | |
| TW201135926A (en) | Growth of planar non-polar {10-10} m-plane gallium nitride with hydride vapor phase epitaxy (HVPE) | |
| CN111809154B (en) | Method for preparing high-quality silicon-based aluminum nitride template | |
| WO2003073484A1 (en) | Crystal manufacturing method | |
| JP2022507504A (en) | Transition from III-N to rare earths in semiconductor structures | |
| CN108111142B (en) | Surface acoustic wave device based on silicon carbide substrate/zinc oxide or zinc oxide-doped film and preparation method thereof | |
| JP2004111848A (en) | Sapphire substrate, epitaxial substrate using it, and its manufacturing method | |
| WO2022053038A1 (en) | Method for growing aln single crystal film and surface acoustic wave resonator having film | |
| CN108010956A (en) | N polar surfaces high frequency GaN rectifier epitaxial structures and preparation method thereof on a kind of silicon substrate | |
| CN113948389B (en) | Silicon-based AlGaN/GaN HEMT based on SiSn epitaxial layer on back surface of substrate and preparation method | |
| Lundin et al. | Study of initial stages of the GaN growth on sapphire substrates | |
| CN107425821B (en) | Low-stress-state monocrystalline AlN for acoustic wave device and preparation and application thereof | |
| CN110828291A (en) | GaN/AlGaN heterojunction material based on single crystal diamond substrate and preparation method thereof | |
| CN118613133A (en) | Method for growing high-quality Al (Sc) N thick film on Si substrate | |
| CN1302529C (en) | Three buffer layer method for preparing high quality zinc oxide monocrystalline film | |
| KR20180040854A (en) | Fabrication method of multilayer film, and multilayer film, and semiconductor device using thereof | |
| KR102556712B1 (en) | Method of manufacturing AlxGa1-xN (0.5≤x≤1) piezoelectric thin films with high purity and their apparatus using the thin film | |
| TW200907124A (en) | Method for forming group-III nitride semiconductor epilayer on silicon substrate | |
| CN106711020B (en) | Nitridation method of substrate and preparation method of gallium nitride buffer layer | |
| CN114203529B (en) | Aluminum nitride epitaxial structure, preparation method thereof and semiconductor device | |
| CN113410352B (en) | Composite AlN template and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |