CN111653473A - Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation - Google Patents
Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation Download PDFInfo
- Publication number
- CN111653473A CN111653473A CN202010339245.2A CN202010339245A CN111653473A CN 111653473 A CN111653473 A CN 111653473A CN 202010339245 A CN202010339245 A CN 202010339245A CN 111653473 A CN111653473 A CN 111653473A
- Authority
- CN
- China
- Prior art keywords
- layer
- gallium nitride
- silicon
- heat dissipation
- microwave device
- 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.)
- Granted
Links
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 132
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000010703 silicon Substances 0.000 title claims abstract description 111
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 110
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 239000000463 material Substances 0.000 title claims abstract description 63
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 56
- 230000004888 barrier function Effects 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 239000002131 composite material Substances 0.000 claims abstract description 16
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 40
- 238000002955 isolation Methods 0.000 claims description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 12
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 12
- RNQKDQAVIXDKAG-UHFFFAOYSA-N aluminum gallium Chemical compound [Al].[Ga] RNQKDQAVIXDKAG-UHFFFAOYSA-N 0.000 claims description 11
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- 229910002704 AlGaN Inorganic materials 0.000 claims description 7
- -1 indium aluminum nitrogen Chemical compound 0.000 claims description 7
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 230000007704 transition Effects 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 9
- 230000006911 nucleation Effects 0.000 description 9
- 238000010899 nucleation Methods 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000001020 plasma etching Methods 0.000 description 5
- 238000003631 wet chemical etching Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 150000003376 silicon Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004891 communication Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 230000005533 two-dimensional electron gas Effects 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- H01L21/02373—Group 14 semiconducting materials
- H01L21/02381—Silicon, silicon germanium, germanium
-
- 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
- H01L21/02441—Group 14 semiconducting materials
- H01L21/02444—Carbon, e.g. diamond-like carbon
-
- 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
- H01L21/02441—Group 14 semiconducting materials
- H01L21/02447—Silicon carbide
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3738—Semiconductor materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/20—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only AIIIBV compounds
- H01L29/2003—Nitride compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/778—Field effect transistors with two-dimensional charge carrier gas channel, e.g. HEMT ; with two-dimensional charge-carrier layer formed at a heterojunction interface
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/86—Types of semiconductor device ; Multistep manufacturing processes therefor controllable only by variation of the electric current supplied, or only the electric potential applied, to one or more of the electrodes carrying the current to be rectified, amplified, oscillated or switched
- H01L29/861—Diodes
- H01L29/872—Schottky diodes
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Junction Field-Effect Transistors (AREA)
Abstract
The invention discloses a silicon-based gallium nitride microwave device material structure with enhanced heat dissipation, which is characterized by comprising the following components in percentage by weight: a silicon substrate layer; the high-thermal-conductivity dielectric layer is positioned on the upper surface of the silicon substrate layer; the buffer layer is positioned on the upper surface of the high-heat-conductivity dielectric layer; the channel layer is positioned on the upper surface of the buffer layer; and the composite barrier layer is positioned on the upper surface of the channel layer so as to form a silicon-based gallium nitride microwave device material structure with enhanced heat dissipation. According to the silicon-based gallium nitride microwave device material structure with enhanced heat dissipation, the bonding between the silicon substrate layer and the buffer layer is realized by adopting the high-heat-conductivity dielectric layer, so that the high bonding strength, the high mechanical strength and the high stability are maintained, the thermal resistance of the device is reduced, and the heat dissipation performance of the silicon-based gallium nitride microwave device is improved.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a silicon-based gallium nitride microwave device material structure with enhanced heat dissipation.
Background
With the development of microelectronic technology, the third generation wide bandgap semiconductor material represented by gallium nitride has physical properties such as larger bandgap, higher critical breakdown electric field, higher electron saturation drift velocity, stable chemical properties, high temperature resistance, radiation resistance and the like, an electronic device manufactured by using the gallium nitride material can further reduce the chip area, improve the working frequency, improve the working temperature, reduce the on-resistance, improve the breakdown voltage and the like, and the gallium nitride material has great potential in the aspect of manufacturing microwave devices.
Gallium nitride and aluminum gallium nitrogen, indium aluminum nitrogen and the like in the same material system with the gallium nitride have high polarization coefficients, a heterostructure formed by the gallium nitride and the aluminum gallium nitrogen or the indium aluminum nitrogen with the forbidden bandwidth larger than that of the gallium nitride can form two-dimensional electron gas, and more than 1500cm can be obtained at room temperature2The electron mobility of the/V.s reaches 1.5 × 10cm7Saturated electron velocity sum of more than 1 × 10 per second13cm-2Thereby a high-speed schottky diode developed based on a gallium nitride material (schottky barrier diode,SBD for short) and High Electron mobility transistor (HEMT for short) devices can have lower on-resistance and higher output current. In addition, the higher critical breakdown electric field intensity of the gallium nitride material can enable the electronic device to have higher breakdown voltage, so that the device can work under higher working voltage, and the device has higher microwave output power density. Gallium nitride devices have higher power added efficiency and thus lower energy losses than silicon or gallium arsenide microwave electronic devices of equivalent output power.
Due to the immaturity of gallium nitride free-standing substrate technology, gallium nitride-based materials are mainly deposited on foreign substrates in current gallium nitride microwave devices. The substrates used so far for the growth of gallium nitride materials are mainly silicon carbide and silicon. The silicon carbide-based gallium nitride device benefits from smaller lattice mismatch of silicon carbide and gallium nitride and higher heat conduction performance of silicon carbide, has lower thermal resistance and higher output power density, is developed earlier and has mature technology. Microwave devices of silicon carbide based gallium nitride have been widely used in the fields of military radars, satellites, communication base stations, etc. However, the cost of silicon carbide based gan devices is relatively high due to the relatively high price and relatively small size of the silicon carbide substrate. Due to the advantages of large size and low cost of the silicon substrate wafer and the scale production of a silicon production line, the silicon-based gallium nitride device has low cost and high cost performance. The silicon-based gallium nitride microwave device is expected to be applied to mobile communication terminals such as 5G communication base stations, mobile phones and the like in a large scale.
However, one important drawback of silicon-based gallium nitride devices is the relatively high thermal resistance and thus poor heat dissipation compared to silicon carbide-based gallium nitride devices, thereby limiting the output power density and efficiency of silicon-based gallium nitride microwave devices. There are two physical mechanisms with poor heat dissipation performance. Firstly, the thermal conductivity of the silicon substrate is relatively poor, and the room temperature thermal conductivity value of a typical silicon carbide substrate is 4.0W/cm.K, while the silicon substrate is only 1.5W/cm.K; secondly, since the lattice mismatch between silicon and gallium nitride crystal materials is large, a very thick nucleation layer and transition layer, such as an aluminum gallium nitride material with gradually changed aluminum components or an aluminum nitride/gallium nitride superlattice material, need to be inserted between the active structure of the gallium nitride device and the silicon substrate, and the crystal materials of the nucleation layer and the transition layer have poor quality, many defects, and poor thermal conductivity. Therefore, the heat dissipation performance of the silicon-based gallium nitride microwave device needs to be improved, and the two problems need to be solved.
At present, the method for improving the heat dissipation performance of the silicon-based gallium nitride microwave device mainly has several technical routes:
1. after the device bare chip process is finished, the silicon substrate is thinned as much as possible, and then the device with the thinned substrate is transferred to a heat sink with high heat conductivity after being scribed. Most of the products of the silicon-based gallium nitride microwave devices at present are silicon substrates thinned to 100 μm, and the technology under development is the silicon substrate thinned to 50 μm. For example, "a.plantalli, a.nanni, c.lanzieri," Thermal floor of AlGaN/GaN HEMT on silicon microstructure technology, "6 th European Microwave Integrated Circuit reference, oct.2011", proposes a method for improving the heat dissipation performance of a device by thinning a silicon substrate, which has a disadvantage that the difficulty of the process operation after thinning the silicon substrate is increased, thereby reducing the yield of the device.
2. A layer of high thermal conductivity dielectric material is deposited on the Surface of a GaN-based microwave device, such as "n.tsurumi, h.ueno, t.murata, h.ishida, y.uemoto, t.ueda, k.inoue, t.tanaka," AlNPassivation Over AlGaN/GaN HFETs for Surface Heat Spreading ", ieee transactions on Electron Devices, vol.57, No.5, pp.980-985, May 2010" a layer of aluminum nitride on the Surface of a GaN-based microwave device, "z.lin, c.liu, c.zhou, y.chai, m.zhou and pe," Improved for electrons with a layer of silicon nitride, GaN-based microwave device, "johnowurdon, GaN-silicon nitride", and "nitride electronics, Electron beam", and "GaN-silicon nitride", and GaN-silicon nitride. The deposition of a layer of nano-grain diamond or the like on the surface of a gallium nitride microwave device is proposed by the IEEEElectron device drivers, Vol.33.No.1, pp.23-25, Jan.2012 ", and the method for depositing a high thermal conductivity dielectric material on the surface of a gallium nitride microwave device has the following disadvantages: these high thermal conductivity materials tend to introduce additional stress, affect device performance, or cause a reduction in the long term reliability of the device.
3. Optimizing the layout design of the silicon-based gallium nitride microwave device, such as "K.Belkaemi and R.hoc," effective 3D-TLM Modeling and Simulation for the thermal Management of microwave AlGaN/GaN HEMT Used in High Power Amplifiers SSPA, "Journal of Low Power Electronics and Applications, Vol.8, No.23,1-19,2018" proposes a method of increasing the pitch of the gate fingers, reducing the gate density, and reducing the heating source density, which has the disadvantages of increasing the area of the device and having low heat dissipation effect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a silicon-based gallium nitride microwave device material structure with enhanced heat dissipation.
One embodiment of the present invention provides a heat dissipation enhanced silicon-based gallium nitride microwave device material structure, which comprises:
a silicon substrate layer;
the high-thermal-conductivity dielectric layer is positioned on the upper surface of the silicon substrate layer;
the buffer layer is positioned on the upper surface of the high-heat-conductivity dielectric layer;
the channel layer is positioned on the upper surface of the buffer layer;
and the composite barrier layer is positioned on the upper surface of the channel layer so as to form a material structure of the silicon-based gallium nitride microwave device.
In one embodiment of the invention, the high-thermal-conductivity dielectric layer comprises aluminum nitride, boron nitride, silicon carbide or diamond, and the thickness is 20-20000 nm.
In an embodiment of the invention, the buffer layer includes gallium nitride, aluminum gallium nitride or aluminum nitride, and the thickness is 100-5000 nm.
In an embodiment of the invention, the channel layer is gallium nitride and has a thickness of 10 to 1000 nm.
In one embodiment of the invention, the composite barrier layer includes an isolation layer and a core barrier layer, wherein,
the isolation layer is positioned on the upper surface of the channel layer;
the core barrier layer is positioned on the upper surface of the isolation layer.
In one embodiment of the invention, the composite barrier layer includes a core barrier layer and a cap layer, wherein,
the core barrier layer is positioned on the upper surface of the channel layer;
the cap layer is located on the upper surface of the core barrier layer.
In one embodiment of the invention, the composite barrier layer includes an isolation layer, a core barrier layer, and a cap layer, wherein,
the isolation layer is positioned on the upper surface of the channel layer;
the core barrier layer is positioned on the upper surface of the isolation layer;
the cap layer is located on the upper surface of the core barrier layer.
In an embodiment of the invention, according to any one of the above silicon-based gallium nitride microwave device material structure with enhanced heat dissipation, the isolation layer is aluminum nitride and has a thickness of 0.5 to 1.5 nm.
In an embodiment of the invention, according to any one of the above heat dissipation-enhanced silicon-based gallium nitride microwave device material structures, the core barrier layer is aluminum gallium nitride, wherein the aluminum component is 0.2-0.4, and the thickness is 10-30 nm;
or indium aluminum nitrogen, wherein the indium component is 0.1-0.2, and the thickness is 5-30 nm;
or aluminum nitride with a thickness of 2-10 nm.
In an embodiment of the invention, according to any one of the above heat dissipation-enhanced silicon-based gallium nitride microwave device material structures, the cap layer is gallium nitride, and the thickness is 1-3 nm;
or silicon nitride with a thickness of 1-10 nm.
Compared with the prior art, the invention has the beneficial effects that:
according to the silicon-based gallium nitride microwave device material structure with enhanced heat dissipation, the bonding between the silicon substrate layer and the buffer layer is realized by adopting the high-heat-conductivity dielectric layer, so that the high bonding strength, the high mechanical strength and the high stability are maintained, the thermal resistance of the device is reduced, and the heat dissipation performance of the silicon-based gallium nitride microwave device is improved.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Drawings
Fig. 1 is a schematic structural diagram of a material structure of a silicon-based gallium nitride microwave device with enhanced heat dissipation according to an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of another structure of a silicon-based GaN microwave device with enhanced heat dissipation according to an embodiment of the invention;
FIG. 3 is a schematic structural diagram of a further structure of a heat-dissipation-enhanced silicon-based gallium nitride microwave device material provided in an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a further structure of a silicon-based gallium nitride microwave device material with enhanced heat dissipation provided by an embodiment of the invention;
fig. 5a to 5l are schematic flow charts of a method for manufacturing a structure of a silicon-based gallium nitride microwave device material with enhanced heat dissipation according to an embodiment of the present invention.
Description of reference numerals:
1-a silicon substrate layer; 2-a high thermal conductivity dielectric layer; 3-a buffer layer; 4-a channel layer; 5-a composite barrier layer; 51-an isolation layer; 52-core barrier layer; 53-cap layer; 10-a first wafer; 20-a second wafer; 30-a third wafer; 40-a fourth wafer; 60-a sixth wafer; 70-a seventh wafer; 80-eighth wafer; 90-ninth wafer; 100-tenth wafer; 110-eleventh wafer; 120-twelfth wafer; 11-a high-resistance silicon substrate layer; 12-a nucleation layer; 13-a transition layer; 21-a first silicon dioxide layer; 31-a silicon wafer; 32-a second silicon dioxide layer; 91-a first aluminum nitride layer; 101-second aluminum nitride layer.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example one
The method for improving the heat dissipation performance of the silicon-based gallium nitride microwave device comprises the following steps: 1. after the device bare chip process is finished, the silicon substrate is thinned as much as possible, but the process operation difficulty after the silicon substrate is thinned is increased, so that the yield of the device is reduced; 2. the method has the disadvantages that a layer of high-heat-conductivity dielectric material is deposited on the surface of the silicon-based gallium nitride microwave device, and the method has the disadvantages that the high-heat-conductivity material often brings extra stress, influences the performance of the device or reduces the long-term reliability of the device; 3. the layout design of the silicon-based gallium nitride microwave device is optimized, and the method has the defects that the area of the device is increased, and in addition, the heat dissipation effect is not high. Based on the above existing problems, in order to reduce the channel temperature of the device during operation and improve the performance of the device, please refer to fig. 1, where fig. 1 is a schematic structural diagram of a heat dissipation enhanced silicon-based gallium nitride microwave device material structure provided in an embodiment of the present invention, this embodiment proposes a heat dissipation enhanced silicon-based gallium nitride microwave device material structure, and the heat dissipation enhanced silicon-based gallium nitride microwave device material structure includes:
a silicon substrate layer 1;
the high-thermal-conductivity dielectric layer 2 is positioned on the upper surface of the silicon substrate layer 1;
the buffer layer 3 is positioned on the upper surface of the high-heat-conductivity dielectric layer 2;
a channel layer 4 on an upper surface of the buffer layer 3;
and the composite barrier layer 5 is positioned on the upper surface of the channel layer 4 to form a silicon-based gallium nitride microwave device material structure with enhanced heat dissipation.
Preferably, the silicon substrate layer 1 is high-resistance silicon, the doping type is n-type or p-type, the resistivity is 3000-30000 omega-cm, and the crystal orientation of the silicon substrate is [111 ]. More preferably, the resistivity is 5000 Ω · cm.
Preferably, the high thermal conductivity dielectric layer 2 comprises aluminum nitride, boron nitride, silicon carbide or diamond, and the thickness is 20-20000 nm. More preferably, the high thermal conductivity dielectric layer 2 is aluminum nitride and has a thickness of 1000 nm.
Preferably, the buffer layer 3 comprises gallium nitride, aluminum gallium nitride or aluminum nitride, and the thickness is 100-5000 nm. More preferably, the buffer layer 3 is gallium nitride and has a thickness of 1000 nm.
Preferably, the channel layer 4 is gallium nitride and has a thickness of 10 to 1000 nm. More preferably, the channel layer 4 is gallium nitride with a thickness of 300 nm.
Further, referring to fig. 2, fig. 2 is a schematic structural diagram of another heat dissipation enhanced gan-based microwave device material structure according to an embodiment of the present invention, in which the composite barrier layer 5 of the present embodiment includes an isolation layer 51 and a core barrier layer 52, wherein,
an isolation layer 51 on an upper surface of the channel layer 4;
and a core barrier layer 52 on the upper surface of the isolation layer 51.
Preferably, the isolation layer 51 is aluminum nitride and has a thickness of 0.5 to 1.5 nm. More preferably, the spacer layer 51 is aluminum nitride and has a thickness of 1 nm.
Preferably, the core barrier layer 52 is AlGaN, wherein the aluminum component is 0.2-0.4 and the thickness is 10-30 nm; or indium aluminum nitrogen, wherein the indium component is 0.1-0.2, and the thickness is 5-30 nm; or aluminum nitride with a thickness of 2-10 nm. More preferably, core barrier layer 52 is aluminum gallium nitride, wherein the composition of aluminum is 0.25 and the thickness is 20 nm.
Alternatively, referring to fig. 3, fig. 3 is a schematic structural diagram of a further silicon-based gallium nitride microwave device material structure with enhanced heat dissipation provided in the embodiment of the present invention, in which the composite barrier layer 5 of the present embodiment includes a core barrier layer 52 and a cap layer 53, wherein,
a core barrier layer 52 on an upper surface of the channel layer 4;
a cap layer 53 is located on the upper surface of the core barrier layer 52.
Preferably, the core barrier layer 52 is AlGaN, wherein the aluminum component is 0.2-0.4 and the thickness is 10-30 nm; or indium aluminum nitrogen, wherein the indium component is 0.1-0.2, and the thickness is 5-30 nm; or aluminum nitride with a thickness of 2-10 nm. More preferably, core barrier layer 52 is aluminum gallium nitride, wherein the composition of aluminum is 0.25 and the thickness is 20 nm.
Preferably, the cap layer 53 is gallium nitride and has a thickness of 1 to 3 nm; or silicon nitride with a thickness of 1-10 nm. More preferably, cap layer 53 is gallium nitride and is 3nm thick.
Alternatively, referring to fig. 4, fig. 4 is a schematic structural diagram of a further heat dissipation enhanced silicon-based gallium nitride microwave device material structure provided in the embodiment of the present invention, in which the composite barrier layer 5 of the present embodiment includes an isolation layer 51, a core barrier layer 52 and a cap layer 53, wherein,
an isolation layer 51 on an upper surface of the channel layer 4;
a core barrier layer 52 on the upper surface of the isolation layer 51;
a cap layer 53 is located on the upper surface of the core barrier layer 52.
Preferably, the isolation layer 51 is aluminum nitride and has a thickness of 0.5 to 1.5 nm. More preferably, the spacer layer 51 is aluminum nitride and has a thickness of 1 nm.
Preferably, the core barrier layer 52 is AlGaN, wherein the aluminum component is 0.2-0.4 and the thickness is 10-30 nm; or indium aluminum nitrogen, wherein the indium component is 0.1-0.2, and the thickness is 5-30 nm; or aluminum nitride with a thickness of 2-10 nm. More preferably, core barrier layer 52 is aluminum gallium nitride, wherein the composition of aluminum is 0.25 and the thickness is 20 nm.
Preferably, the cap layer 53 is gallium nitride and has a thickness of 1 to 3 nm; or silicon nitride with a thickness of 1-10 nm. More preferably, cap layer 53 is gallium nitride and is 3nm thick.
In the conventional material structure of silicon-based gallium nitride, because a large lattice constant mismatch exists between a silicon substrate layer and a gallium nitride buffer layer, an aluminum nitride nucleation layer and a transition layer are introduced, wherein the transition layer can be aluminum gallium nitride or aluminum nitride/gallium nitride superlattice. However, the crystal quality of the aluminum nitride nucleation layer and the transition layer is poor, the dislocation density is high, the thermal conductivity is poor, and the heat dissipation performance of the silicon-based gallium nitride microwave device is seriously influenced. In the material structure of the silicon-based gallium nitride microwave device with enhanced heat dissipation provided by the embodiment, the aluminum nitride nucleation layer and the transition layer are not arranged between the silicon substrate layer 1 and the buffer layer 3, so that the thermal resistance of the device is reduced, the thermal conductivity of the device is improved, the working channel temperature of the device is reduced, and the performance of the device is improved.
Meanwhile, in the material structure of the conventional silicon-based gallium nitride, because the silicon substrate layer and the gallium nitride buffer layer have larger lattice mismatch, the two materials are difficult to be directly bonded, and a stable material structure of the silicon-based gallium nitride microwave device is formed. In the embodiment, the bonding between the silicon substrate layer 1 and the buffer layer 3 is realized by adopting the high-thermal-conductivity dielectric layer 2, so that the high bonding strength, the high mechanical strength and the high stability are maintained, and the thermal resistance of the device is reduced, thereby improving the heat dissipation performance of the silicon-based gallium nitride microwave device, reducing the working channel temperature of the device and improving the performance of the device.
In summary, the heat dissipation enhanced silicon-based gallium nitride microwave device material structure provided by the embodiment: the high-thermal-conductivity dielectric layer 2 is manufactured on the upper surface of the silicon substrate layer 1, so that the mechanical strength, the stability and the thermal conductivity between the III-group nitride buffer layer 3 and the silicon substrate layer 1 are improved; the buffer layer 3 is manufactured on the upper surface of the high-thermal-conductivity dielectric layer 2, and a nucleation layer or a transition layer with higher dislocation density and poorer thermal conductivity is not arranged between the buffer layer and the high-thermal-conductivity dielectric layer 2, so that the thermal resistance of the device is reduced and the thermal conductivity of the device is improved; the channel layer 4 is manufactured on the upper surface of the buffer layer 3 and is used for improving a conductive channel for a device; the composite barrier layer 5 is manufactured on the upper surface of the channel layer 4, two-dimensional electron gas is formed at the interface between the composite barrier layer 5 and the channel layer 4 and is used as a conductive channel of the device, and the electrical characteristics of the silicon-based gallium nitride microwave device are further improved through the isolating layer 51 or the cap layer 53. The silicon-based gallium nitride microwave device material structure with enhanced heat dissipation provided by the embodiment also has the advantages of compatibility with the existing silicon production line, capability of mass production, high yield and high reliability. The silicon-based gallium nitride microwave device material structure with enhanced heat dissipation provided by the embodiment can be applied to the fields of chips, systems and the like of radio frequency, microwave and millimeter wave.
Example two
On the basis of the first embodiment, please refer to fig. 5a to 5l, where fig. 5a to 5l are schematic flow diagrams of a method for preparing a heat dissipation-enhanced silicon-based gallium nitride microwave device material structure according to an embodiment of the present invention, and this embodiment proposes a method for preparing a heat dissipation-enhanced silicon-based gallium nitride microwave device material structure for the heat dissipation-enhanced silicon-based gallium nitride microwave device material structure described in fig. 4 in the first embodiment, where the method includes the following steps:
step 14, adopting MOCVD equipment and technology to epitaxially grow a 300 nm-thick gallium nitride channel layer 4 on the gallium nitride buffer layer 3, wherein the gallium nitride channel layer 4 is unintentionally doped;
step 15, adopting MOCVD equipment and technology to epitaxially grow an aluminum nitride isolation layer 51 with the thickness of 1nm on the gallium nitride channel layer 4;
and step 17, epitaxially growing a gallium nitride cap layer 53 with the thickness of 3nm on the core barrier layer 52 by using MOCVD equipment and technology to manufacture and form the first wafer 10.
And step 3, referring to fig. 5c again, depositing a second silicon dioxide layer 32 with a thickness of 250nm on the upper surface of a silicon wafer 31 by using PECVD equipment and technology to form a third wafer 30, wherein the size of the silicon wafer 31 is 8 inches, the thickness is 725 μm, the resistivity is 10 Ω · cm, and the crystal orientation is [100 ].
step 6, referring to fig. 5f again, removing the aluminum nitride nucleation layer 12 in the sixth wafer 60 manufactured in step 5 by using a wet chemical etching technique or a plasma etching technique to manufacture a seventh wafer 70;
step 7, referring to fig. 5g again, removing the aluminum nitride/gallium nitride superlattice transition layer 13 in the seventh wafer 70 manufactured in step 6 by using a wet chemical etching technology or a plasma etching technology to manufacture an eighth wafer 80;
step 8, please refer to fig. 5h again, a magnetron sputtering technique is adopted, and a first aluminum nitride layer 91 with the thickness of 500nm is deposited on the upper surface of the eighth wafer 80 manufactured in the step 7, so as to manufacture and form a ninth wafer 90;
step 9, please refer to fig. 5i again, depositing a second aluminum nitride layer 101 with a thickness of 500nm on the surface of a silicon substrate layer 1 by adopting a magnetron sputtering technology to manufacture and form a tenth wafer 100, wherein the size of the silicon substrate layer 1 is 8 inches, the thickness is 725 micrometers, the resistivity is 5000 Ω · cm, and the crystal orientation is [111 ];
It should be noted that the preparation processes in fig. 2 and fig. 3 of this embodiment are similar to those in fig. 4, and are not repeated herein.
The method for preparing a heat-dissipation-enhanced silicon-based gallium nitride microwave device material structure provided in this embodiment may be implemented in the embodiment of the heat-dissipation-enhanced silicon-based gallium nitride microwave device material structure described in the first embodiment, and the implementation principle and technical effect are similar, and are not described herein again.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A silicon-based gallium nitride microwave device material structure with enhanced heat dissipation is characterized by comprising:
a silicon substrate layer (1);
the high-heat-conductivity dielectric layer (2) is positioned on the upper surface of the silicon substrate layer (1);
the buffer layer (3) is positioned on the upper surface of the high-heat-conductivity dielectric layer (2);
a channel layer (4) located on an upper surface of the buffer layer (3);
and the composite barrier layer (5) is positioned on the upper surface of the channel layer (4) so as to form the heat dissipation enhanced silicon-based gallium nitride microwave device material structure.
2. The microwave device material structure with enhanced heat dissipation and silicon-based gallium nitride according to claim 1, wherein the high thermal conductivity dielectric layer (2) comprises aluminum nitride, boron nitride, silicon carbide or diamond, and the thickness is 20-20000 nm.
3. The microwave device material structure of silicon-based gallium nitride with enhanced heat dissipation according to claim 1, wherein the buffer layer (3) comprises gallium nitride, aluminum gallium nitride or aluminum nitride, and the thickness is 100-5000 nm.
4. The microwave device material structure of silicon-based gallium nitride with enhanced heat dissipation of claim 1, wherein the channel layer (4) is gallium nitride with a thickness of 10-1000 nm.
5. The microwave device material structure on silicon based gallium nitride with enhanced heat dissipation according to claim 1, characterized in that the composite barrier layer (5) comprises an isolation layer (51) and a core barrier layer (52), wherein,
the isolation layer (51) is positioned on the upper surface of the channel layer (4);
the core barrier layer (52) is positioned on the upper surface of the isolation layer (51).
6. The microwave device material structure for Si-based gallium nitride with enhanced heat dissipation according to claim 1, characterized in that the composite barrier layer (5) comprises a core barrier layer (52) and a cap layer (53), wherein,
the core barrier layer (52) is positioned on the upper surface of the channel layer (4);
the cap layer (53) is positioned on the upper surface of the core barrier layer (52).
7. The microwave device material structure for Si-based gallium nitride with enhanced heat dissipation according to claim 1, characterized in that the composite barrier layer (5) comprises an isolation layer (51), a core barrier layer (52) and a cap layer (53), wherein,
the isolation layer (51) is positioned on the upper surface of the channel layer (4);
the core barrier layer (52) is positioned on the upper surface of the isolation layer (51);
the cap layer (53) is positioned on the upper surface of the core barrier layer (52).
8. The microwave device material structure for silicon-based gallium nitride with enhanced heat dissipation according to any of claims 5 or 7, wherein the isolation layer (51) is aluminum nitride and has a thickness of 0.5-1.5 nm.
9. The microwave device material structure of Si-based GaN with enhanced heat dissipation according to any of claims 5 to 7, characterized in that the core barrier layer (52) is AlGaN, wherein the composition of Al is 0.2-0.4 and the thickness is 10-30 nm;
or indium aluminum nitrogen, wherein the indium component is 0.1-0.2, and the thickness is 5-30 nm;
or aluminum nitride with a thickness of 2-10 nm.
10. The microwave device material structure with enhanced heat dissipation and silicon-based gallium nitride as claimed in any one of claims 6 or 7, wherein the cap layer (53) is gallium nitride and has a thickness of 1-3 nm;
or silicon nitride with a thickness of 1-10 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010339245.2A CN111653473B (en) | 2020-04-26 | 2020-04-26 | Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010339245.2A CN111653473B (en) | 2020-04-26 | 2020-04-26 | Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111653473A true CN111653473A (en) | 2020-09-11 |
| CN111653473B CN111653473B (en) | 2023-10-13 |
Family
ID=72344722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010339245.2A Active CN111653473B (en) | 2020-04-26 | 2020-04-26 | Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111653473B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981444A (en) * | 2021-10-18 | 2022-01-28 | 北京大学东莞光电研究院 | Thin-layer device and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5272104A (en) * | 1993-03-11 | 1993-12-21 | Harris Corporation | Bonded wafer process incorporating diamond insulator |
| CN102064255A (en) * | 2010-12-10 | 2011-05-18 | 西安神光安瑞光电科技有限公司 | LED (Light Emitting Diode) and manufacturing method thereof |
| CN102569390A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院微电子研究所 | High-breakdown gallium nitride-based field effect transistor device and manufacturing method thereof |
| US20140312424A1 (en) * | 2011-11-04 | 2014-10-23 | The Silanna Group Pty Ltd. | Method of producing a silicon-on-insulator article |
| CN104143567A (en) * | 2013-05-09 | 2014-11-12 | Lg伊诺特有限公司 | Semiconductor device and method of manufacturing the same |
| CN105140122A (en) * | 2015-08-10 | 2015-12-09 | 中国电子科技集团公司第五十五研究所 | Method for improving cooling performance of GaN high-electron mobility transistor (HEMT) device |
| CN107482032A (en) * | 2017-08-10 | 2017-12-15 | 佛山市国星半导体技术有限公司 | A kind of MicroLED chips for full-color display and preparation method thereof |
| CN108389903A (en) * | 2018-03-01 | 2018-08-10 | 中国科学院微电子研究所 | AlGaN/GaN high electron mobility transistor and preparation method with graphene heat dissipating layer |
| US20180286664A1 (en) * | 2017-03-31 | 2018-10-04 | Globalwafers Co., Ltd. | Epitaxial substrate and method of manufacturing the same |
-
2020
- 2020-04-26 CN CN202010339245.2A patent/CN111653473B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5272104A (en) * | 1993-03-11 | 1993-12-21 | Harris Corporation | Bonded wafer process incorporating diamond insulator |
| CN102064255A (en) * | 2010-12-10 | 2011-05-18 | 西安神光安瑞光电科技有限公司 | LED (Light Emitting Diode) and manufacturing method thereof |
| CN102569390A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院微电子研究所 | High-breakdown gallium nitride-based field effect transistor device and manufacturing method thereof |
| US20140312424A1 (en) * | 2011-11-04 | 2014-10-23 | The Silanna Group Pty Ltd. | Method of producing a silicon-on-insulator article |
| CN104143567A (en) * | 2013-05-09 | 2014-11-12 | Lg伊诺特有限公司 | Semiconductor device and method of manufacturing the same |
| CN105140122A (en) * | 2015-08-10 | 2015-12-09 | 中国电子科技集团公司第五十五研究所 | Method for improving cooling performance of GaN high-electron mobility transistor (HEMT) device |
| US20180286664A1 (en) * | 2017-03-31 | 2018-10-04 | Globalwafers Co., Ltd. | Epitaxial substrate and method of manufacturing the same |
| CN107482032A (en) * | 2017-08-10 | 2017-12-15 | 佛山市国星半导体技术有限公司 | A kind of MicroLED chips for full-color display and preparation method thereof |
| CN108389903A (en) * | 2018-03-01 | 2018-08-10 | 中国科学院微电子研究所 | AlGaN/GaN high electron mobility transistor and preparation method with graphene heat dissipating layer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113981444A (en) * | 2021-10-18 | 2022-01-28 | 北京大学东莞光电研究院 | Thin-layer device and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111653473B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7033912B2 (en) | Silicon carbide on diamond substrates and related devices and methods | |
| US11942518B2 (en) | Reduced interfacial area III-nitride material semiconductor structures | |
| US20210126120A1 (en) | Modification of electric fields of compound semiconductor devices | |
| US8558285B2 (en) | Method using low temperature wafer bonding to fabricate transistors with heterojunctions of Si(Ge) to III-N materials | |
| CN111512415B (en) | System and method for engineering integrated devices on a substrate | |
| US20150123139A1 (en) | High electron mobility transistor and method of manufacturing the same | |
| WO2021017954A1 (en) | Microelectronic device and manufacturing method for microelectronic device | |
| CN112216739B (en) | Low-thermal-resistance silicon-based gallium nitride microwave millimeter wave device material structure and preparation method | |
| TWI464877B (en) | Nitride-based heterostructure field effect transistor having high efficiency | |
| CN111653473B (en) | Silicon-based gallium nitride microwave device material structure with enhanced heat dissipation | |
| TWI523148B (en) | Method for increasing breakdown voltage of hemt device | |
| CN213212169U (en) | Epitaxial structure of semiconductor device and semiconductor device | |
| Parvais et al. | Advanced transistors for high frequency applications | |
| Kuzuhara et al. | GaAs-based high-frequency and high-speed devices | |
| CN108493111B (en) | Method, semi-conductor device manufacturing method | |
| CN113555330A (en) | Gallium nitride material structure with back through hole for enhancing heat dissipation and preparation method thereof | |
| JP2003133320A (en) | Thin film semiconductor epitaxial substrate and manufacturing method therefor | |
| CN220233200U (en) | Gallium nitride epitaxial structure | |
| CN216597586U (en) | Enhanced gallium nitride high electron mobility transistor structure | |
| US20230420553A1 (en) | Semiconductor structure and method of manufacture | |
| CN116762177A (en) | Semiconductor structure, preparation method thereof and electronic equipment | |
| CN113644118A (en) | Composite substrate and method for manufacturing same |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |