CN114373836A - Method for recycling sapphire substrate - Google Patents
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- CN114373836A CN114373836A CN202111640178.9A CN202111640178A CN114373836A CN 114373836 A CN114373836 A CN 114373836A CN 202111640178 A CN202111640178 A CN 202111640178A CN 114373836 A CN114373836 A CN 114373836A
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- 239000000758 substrate Substances 0.000 title claims abstract description 55
- 229910052594 sapphire Inorganic materials 0.000 title claims abstract description 51
- 239000010980 sapphire Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004064 recycling Methods 0.000 title claims description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 59
- 238000005530 etching Methods 0.000 claims abstract description 46
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003513 alkali Substances 0.000 claims abstract description 39
- 229910002601 GaN Inorganic materials 0.000 claims abstract description 24
- 239000002585 base Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 11
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 55
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 230000010355 oscillation Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910002704 AlGaN Inorganic materials 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- -1 InGaN Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000000861 blow drying Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
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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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- Manufacturing & Machinery (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for recovering a sapphire substrate, which is suitable for a flat sheet or a graphical sapphire substrate, and adopts a method of multiple liquid medicine etching and high-temperature baking to remove gallium nitride related epitaxial materials, and comprises the following steps: 1) etching the gallium nitride-based LED epitaxial wafer by using the alkali liquor A for the first time; 2) baking the LED epitaxial wafer at high temperature for the first time; 3) etching the LED epitaxial wafer by the alkali liquor A for the second time; 4) baking the LED epitaxial wafer at high temperature for the second time; 5) etching the LED epitaxial wafer by using the alkali liquor A for the third time; 6) carrying out acid-base cleaning by SPM for the first time; 7) etching with phosphoric acid liquid; 8) and carrying out acid-base cleaning for the second time by SPM. The surface of the sapphire substrate recovered by the method is clean and free of damage; the LED epitaxial wafer can be reused, so that the production cost of the LED epitaxial wafer is reduced.
Description
Technical Field
The invention relates to the field of photoelectricity, in particular to a method for recycling a sapphire substrate.
Background
Based on sapphire (Al)2O3) The substrate has mature production and processing technology, good device quality and stability, and can be applied to the high-temperature growth process. Sapphire is therefore a popular choice as a growth substrate in the area of GaN-based materials and devices. Especially inCurrently, in the industrial application of GaN-based LEDs, sapphire substrates are still the mainstream. And for the partial products with poor yield in the production of the LED epitaxial wafer, the partial products are scrapped, so that the production cost of the epitaxial wafer is seriously increased. The excellent properties of sapphire materials make it possible to recycle them. The epitaxial layer of the LED epitaxial wafer is removed to obtain the sapphire substrate which can be directly recycled, the sapphire substrate with a clean surface and no damage is critical to the crystal quality of the GaN material epitaxial wafer, and the photoelectric characteristics of an LED product are directly influenced.
At present, various methods for recycling the sapphire substrate exist, but all have certain defects: for example, the epitaxial layer on the sapphire substrate is thinned by mechanical grinding, and the method is suitable for recycling the plane sapphire substrate; the epitaxial layer on the patterned sapphire substrate is removed by using a plasma etching method, and the used etching gas can also damage the pattern on the patterned sapphire substrate; the introduction of corrosive gas under high temperature conditions to decompose gallium nitride requires modification of high temperature ovens used in epitaxial production, which increases the cost of recovery.
Whether the sapphire substrate with a clean surface and no damage can be obtained is very critical in each process technical step of the whole recovery process. Particularly, in the currently used sapphire substrate with micron-sized patterning, before epitaxial growth, an AlN film is sputtered on the substrate, and the recovered sapphire substrate must remove the AlN material between the substrate patterns, otherwise epitaxial process production and product yield are affected.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems in the prior art, the invention provides a recycling method of a sapphire substrate, wherein the sapphire substrate with a clean surface and no damage is obtained by recycling and can be reused, so that the production cost of an LED epitaxial wafer is reduced.
The technical scheme is as follows: the invention discloses a method for recovering a sapphire substrate, which adopts multiple liquid medicine etching and high-temperature baking processes and specifically comprises the following steps:
1) etching the gallium nitride-based LED epitaxial wafer by using the alkali liquor A for the first time;
2) baking the LED epitaxial wafer at high temperature for the first time;
3) etching the LED epitaxial wafer by the alkali liquor A for the second time;
4) baking the LED epitaxial wafer at high temperature for the second time;
5) etching the LED epitaxial wafer by using the alkali liquor A for the third time;
6) carrying out acid-base cleaning by SPM for the first time;
7) etching with phosphoric acid liquid;
8) and carrying out acid-base cleaning for the second time by SPM.
Furthermore, the recycling object is one or more of gallium nitride related III-V compound materials, specifically GaN, InGaN, AlGaN, AlN and other thin film materials.
Further, the thickness of the epitaxial layer of the recovery object is 3 to 10 μm.
Furthermore, the same alkali liquor is used in the step 1), the step 3) and the step 5), and specifically, the alkali liquor A is a sodium hydroxide solution with the mass concentration of 15-50%.
Furthermore, the temperature for etching the epitaxial material on the substrate by the alkali liquor A in the steps 1), 3) and 5) is 50-100 ℃, the etching time is 4-12h, and ultrasonic oscillation is carried out simultaneously, and the ultrasonic frequency is 30 KHz.
Furthermore, the high-temperature baking temperature in the step 2) and the step 4) is 950-.
Further, the SPM acid-base cleaning process conditions in the step 6) and the step 8) are the same, and the acid and the base are H with the mass concentration of 98%2SO4And H2O2The mixture solution of (A) and (B) is H2SO4:H2O2The temperature of the SPM mixed solution for cleaning the sample is 70-90 ℃ and the cleaning time is 3-10min, which is 3: 1.
Furthermore, the phosphoric acid liquor is used for etching in the step 7), and the liquor has the mass concentration of 85 percent by weightIs mixed with 98 percent of sulfuric acid, and the mixture ratio is H3PO4:H2SO4The etching temperature is 100-.
Has the advantages that: the invention has the following advantages:
(1) the method mainly comprises the steps of alkali liquor corrosion, high-temperature baking and phosphoric acid etching, and has high recovery efficiency and low recovery cost.
(2) Step 1) the epitaxial layer is corroded by alkali liquor, the sapphire material cannot be corroded by the alkali liquor, and the corroded epitaxial wafer is baked at high temperature for the first time, so that the epitaxial material on the surface of the substrate can be stripped.
(3) The epitaxial material residue with larger size can still be seen on the surface of the sample after the first baking, the residue on the surface of the sample is corroded by the alkali liquor again in the step 3), and the epitaxial material residue can be effectively removed by matching with the secondary high-temperature baking in the step 4).
(4) And 5) corroding the surface of the sample with the alkali liquor for the third time, wherein on one hand, the small-particle epitaxial material on the surface of the sample is continuously corroded, and on the other hand, the sample is cleaned.
(5) And 6) cleaning the sample with SPM acid and alkali to remove organic matters, particles and other dirt on the surface of the sample introduced in the process, so as to prepare for thoroughly cleaning the epitaxial material on the surface of the substrate in the step 7).
(6) And 7) etching the sample by using the phosphoric acid liquid, particularly etching the patterned sapphire substrate, wherein the epitaxial material, mainly AlN, remained on the surface of the patterned sapphire substrate is completely etched, and the sapphire substrate with a clean surface and no damage is obtained by controlling the temperature and the etching time of the phosphoric acid liquid.
(7) And 8) carrying out SPM acid-base cleaning on the sample again, wherein the SPM acid-base cleaning is taken as the last step of the recovery method, and the purpose is to remove the surface stains of the recovered sapphire substrate again, finally obtain the sapphire substrate with clean and undamaged surface, and directly carry out epitaxial growth again.
Drawings
FIG. 1 is a schematic flow diagram of a recovery process according to the present invention;
FIG. 2 is a schematic view of a sample of an epitaxial wafer to be recovered in example 1;
FIG. 3 is the surface topography of the sample of example 1 after the first 3 steps;
FIG. 4 is the surface topography of the sample of example 1 after the first 5 steps;
FIG. 5 shows the surface topography of the sapphire substrate finally recovered in example 1.
Detailed Description
Fig. 1 is a schematic structural diagram of an LED epitaxial wafer to be recycled according to embodiments 1-3 of the present invention, wherein 01 is a patterned sapphire substrate, and 02 is a GaN-related epitaxial layer;
the LED epitaxial layer grown on the patterned sapphire substrate specifically comprises: the GaN-based LED comprises an AlN material buffer layer, an undoped GaN thin film layer, an N-type doped AlGaN thin film layer, an InGaN/GaN multi-quantum well layer, a P-type doped AlGaN layer and a P-type doped GaN layer.
Collectively referred to herein as GaN-related material epitaxial layers.
Example 1:
referring to fig. 1, the invention discloses a method for recycling a sapphire substrate, wherein a sample is a GaN-based LED epitaxial wafer, comprising the following steps:
1) etching a GaN-based LED epitaxial wafer sample by using alkali liquor A for the first time:
the alkali liquor is sodium hydroxide solution, the solution is prepared in a container with heating and ultrasonic oscillation, the mass concentration of the prepared solution is 15%, the solution is heated to 90 ℃, a sample is put into the sodium hydroxide solution to be corroded for 8 hours, and the ultrasonic oscillation is started, and the ultrasonic frequency is 30 KHz.
2) And (3) baking the sample in a high-temperature vacuum furnace at high temperature:
and (3) cleaning the sample corroded by the alkali liquor with pure water, drying the sample by using a nitrogen gun, putting the sample into a high-temperature vacuum furnace, and baking the sample at high temperature, wherein the temperature of a high-temperature section is 1000 ℃, the pressure of a cavity of the high-temperature furnace is 0mbar/20mbar, two low-pressure states are alternated, the nitrogen flow rate in the baking process is 2000sccm, the hydrogen flow rate is 100sccm, and the high-temperature baking time is kept for 6 hours.
3) And etching the LED epitaxial wafer by using alkali liquor A for the second time:
continuing to use the sodium hydroxide solution obtained in the step 1), wherein the mass concentration of the solution is 15%, heating the solution to 60 ℃, putting the sample into the sodium hydroxide solution for corrosion for 10 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 KHz.
4) Baking the LED epitaxial wafer at high temperature for the second time:
cleaning and blow-drying the sample obtained in the step 3), then placing the sample into a high-temperature vacuum furnace again for high-temperature baking, wherein the temperature of a high-temperature section is 1000 ℃, the pressure of a cavity of the high-temperature furnace is 100mbar/150mbar, the two low-pressure states are alternated, the nitrogen flow rate and the hydrogen flow rate in the baking process are 2000sccm and 100sccm respectively, and the high-temperature baking time is kept for 30 min.
5) Etching the LED epitaxial wafer by alkali liquor A for the third time:
continuing to use the sodium hydroxide solution obtained in the step 3), wherein the mass concentration of the solution is 25%, heating the solution to 60 ℃, putting the sample into the sodium hydroxide solution for corrosion for 8 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 KHz.
6) Carrying out primary SPM acid-base cleaning:
cleaning the sample corroded by the alkali liquor with pure water, drying the sample by a nitrogen gun, and then putting the sample into an SPM acid-base cleaning tank, wherein the SPM cleaning solution is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of the SPM mixture for washing the sample was 80 ℃ and the washing time was 5min, 3: 1.
7) Etching with phosphoric acid liquid:
the sample after the SPM cleaning was spin-dried with a nitrogen spin dryer after being cleaned with pure water. Etching the sample in phosphoric acid solution containing 85% phosphoric acid and 98% sulfuric acid at a ratio of H3PO4:H2SO4The etching solution temperature was 150 ℃ and the cleaning time was 60s, 3: 1. Then cleaning with pure water, and spin-drying with nitrogen spin-drying machine
8) And (3) carrying out acid-base cleaning by SPM for the second time:
finally, thePutting the sample into an SPM acid-base cleaning tank, wherein the cleaning solution of the SPM is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of an SPM mixed solution for cleaning the sample is 80 ℃, and the cleaning time is 5 min; and then, cleaning the sapphire substrate by pure water, and spin-drying the sapphire substrate by using a nitrogen gas spin dryer to obtain the reusable sapphire substrate with clean surface and no damage.
Appearance inspection was performed on the samples in the process and the sapphire substrate obtained by recovery using a metallographic microscope, as shown in fig. 3 to 5, respectively. It can be seen that the method of the present invention can successfully recover the sapphire substrate with clean and undamaged surface.
Example 2:
referring to fig. 1, the invention discloses a method for recycling a sapphire substrate, wherein a sample is a GaN-based LED epitaxial wafer, comprising the following steps:
1) etching a GaN-based LED epitaxial wafer sample by using alkali liquor A for the first time:
the alkali liquor is sodium hydroxide solution, the solution is prepared in a container with heating and ultrasonic oscillation, the mass concentration of the prepared solution is 40%, the temperature of the solution is heated to 70 ℃, a sample is put into the sodium hydroxide solution to be corroded for 8 hours, and the ultrasonic oscillation is started, wherein the ultrasonic frequency is 30 KHz.
2) And (3) baking the sample in a high-temperature vacuum furnace at high temperature:
and (3) cleaning the sample corroded by the alkali liquor with pure water, drying the sample by using a nitrogen gun, putting the sample into a high-temperature vacuum furnace, baking the sample at high temperature, wherein the temperature of a high-temperature section is 1050 ℃, the pressure of a cavity of the high-temperature furnace is 10mbar/30mbar, the two low-pressure states are alternated, the nitrogen flow rate in the baking process is 3000sccm, the hydrogen flow rate is 200sccm, and the high-temperature baking time is kept for 6 hours.
3) And etching the LED epitaxial wafer by using alkali liquor A for the second time:
continuing to use the sodium hydroxide solution obtained in the step 1), wherein the mass concentration of the solution is 40%, heating the solution to 70 ℃, putting the sample into the sodium hydroxide solution for corrosion for 8 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 KHz.
4) Baking the LED epitaxial wafer at high temperature for the second time:
cleaning and blow-drying the sample obtained in the step 3), then placing the sample into a high-temperature vacuum furnace again for high-temperature baking, wherein the temperature of a high-temperature section is 1050 ℃, the pressure of a cavity of the high-temperature furnace is 100mbar/150mbar, the two low-pressure states are alternated, the nitrogen flow is 2000sccm, the hydrogen flow is 100sccm in the baking process, and the high-temperature baking time is kept for 25 min.
5) Etching the LED epitaxial wafer by alkali liquor A for the third time:
continuing to use the sodium hydroxide solution obtained in the step 3), wherein the mass concentration of the solution is 40%, heating the solution to 70 ℃, putting the sample into the sodium hydroxide solution for corrosion for 8 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 KHz.
6) Carrying out primary SPM acid-base cleaning:
cleaning the sample corroded by the alkali liquor with pure water, drying the sample by a nitrogen gun, and then putting the sample into an SPM acid-base cleaning tank, wherein the SPM cleaning solution is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of the SPM mixture for washing the sample was 80 ℃ and the washing time was 5min, 3: 1.
7) Etching with phosphoric acid liquid:
the sample after the SPM cleaning was spin-dried with a nitrogen spin dryer after being cleaned with pure water. Etching the sample in phosphoric acid solution containing 85% phosphoric acid and 98% sulfuric acid at a ratio of H3PO4:H2SO4The etching solution temperature was 150 ℃ and the cleaning time was 60s, 3: 1. Then, the sample was washed with pure water and then spin-dried with a nitrogen spin dryer.
8) And (3) carrying out acid-base cleaning by SPM for the second time:
finally, putting the sample into an SPM acid-base cleaning tank, wherein the cleaning solution of the SPM is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of an SPM mixed solution for cleaning the sample is 80 ℃, and the cleaning time is 5 min; then cleaning the surface with pure water, and spin-drying with a nitrogen gas spin dryer to obtain clean surfaceAnd a damage-free reusable sapphire substrate.
Example 3:
referring to fig. 1, the invention discloses a method for recycling a sapphire substrate, wherein a sample is a GaN-based LED epitaxial wafer, comprising the following steps:
1) etching a GaN-based LED epitaxial wafer sample by using alkali liquor A for the first time:
the alkali liquor is sodium hydroxide solution, the solution is prepared in a container with heating and ultrasonic oscillation, the mass concentration of the prepared solution is 35%, the temperature of the solution is heated to 90 ℃, a sample is put into the sodium hydroxide solution to be corroded for 6 hours, and the ultrasonic oscillation is started, wherein the ultrasonic frequency is 30 KHz.
2) And (3) baking the sample in a high-temperature vacuum furnace at high temperature:
and (3) cleaning the sample corroded by the alkali liquor with pure water, drying the sample by using a nitrogen gun, putting the sample into a high-temperature vacuum furnace, and baking the sample at high temperature, wherein the temperature of a high-temperature section is 1050 ℃, the pressure of a cavity of the high-temperature furnace is 20mbar/50mbar, the two low-pressure states are alternated, the nitrogen flow rate in the baking process is 4000sccm, the hydrogen flow rate is 300sccm, and the high-temperature baking time is kept for 4 hours.
3) And etching the LED epitaxial wafer by using alkali liquor A for the second time:
continuing to use the sodium hydroxide solution obtained in the step 1), wherein the mass concentration of the solution is 35%, heating the solution to 90 ℃, putting the sample into the sodium hydroxide solution for corrosion for 10 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 kHz.
4) Baking the LED epitaxial wafer at high temperature for the second time:
cleaning and blow-drying the sample obtained in the step 3), then placing the sample into a high-temperature vacuum furnace again for high-temperature baking, wherein the temperature of a high-temperature section is 1000 ℃, the pressure of a cavity of the high-temperature furnace is 100mbar/150mbar, the two low-pressure states are alternated, the nitrogen flow rate in the baking process is 4000sccm, the hydrogen flow rate is 300sccm, and the high-temperature baking time is kept for 30 minutes.
5) Etching the LED epitaxial wafer by alkali liquor A for the third time:
continuing to use the sodium hydroxide solution obtained in the step 3), wherein the mass concentration of the solution is 30%, heating the solution to 90 ℃, putting the sample into the sodium hydroxide solution for corrosion for 5 hours, and turning on ultrasonic oscillation, wherein the ultrasonic frequency is 30 KHz.
6) Carrying out primary SPM acid-base cleaning:
cleaning the sample corroded by the alkali liquor with pure water, drying the sample by a nitrogen gun, and then putting the sample into an SPM acid-base cleaning tank, wherein the SPM cleaning solution is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of the SPM mixture for washing the sample was 90 ℃ and the washing time was 4min, 3: 1.
7) Etching with phosphoric acid liquid:
the sample after the SPM cleaning was spin-dried with a nitrogen spin dryer after being cleaned with pure water. Etching the sample in phosphoric acid solution containing 85% phosphoric acid and 98% sulfuric acid at a ratio of H3PO4:H2SO4The etching solution temperature was 200 ℃ and the cleaning time was 40s, 3: 1. Then, the sample was washed with pure water and then spin-dried with a nitrogen spin dryer.
8) And (3) carrying out acid-base cleaning by SPM for the second time:
finally, putting the sample into an SPM acid-base cleaning tank, wherein the cleaning solution of the SPM is H with the mass concentration of 98%2SO4And H2O2The mixture ratio of (A) to (B) is H2SO4:H2O2The temperature of an SPM mixed solution for cleaning the sample is 3:1, and the cleaning time is 4 min; and then, cleaning the sapphire substrate by pure water, and spin-drying the sapphire substrate by using a nitrogen gas spin dryer to obtain the reusable sapphire substrate with clean surface and no damage.
Claims (8)
1. A method for recycling a sapphire substrate is characterized by adopting a multiple-time liquid etching and high-temperature baking process, and specifically comprises the following steps:
1) etching the gallium nitride-based LED epitaxial wafer by using the alkali liquor A for the first time;
2) baking the LED epitaxial wafer at high temperature for the first time;
3) etching the LED epitaxial wafer by the alkali liquor A for the second time;
4) baking the LED epitaxial wafer at high temperature for the second time;
5) etching the LED epitaxial wafer by using the alkali liquor A for the third time;
6) carrying out acid-base cleaning by SPM for the first time;
7) etching with phosphoric acid liquid;
8) and carrying out acid-base cleaning for the second time by SPM.
2. The method according to claim 1, wherein the recycling object is a gallium nitride-related III-V compound material, specifically one or more of GaN, InGaN, AlGaN, AlN, and other thin film materials.
3. The method for recycling a sapphire substrate according to claim 2, wherein the thickness of the epitaxial layer of the recycling object is 3 to 10 μm.
4. The method of recycling a sapphire substrate according to claim 1, wherein: the alkali liquor of the same kind is used in the step 1), the step 3) and the step 5), and the alkali liquor A is a sodium hydroxide solution with the mass concentration of 15-50%.
5. The method of recycling a sapphire substrate according to claim 1 or 4, wherein: in the steps 1), 3) and 5), the temperature for etching the epitaxial material on the substrate by the alkali liquor A is 50-100 ℃, the etching time is 4-12h, and ultrasonic oscillation is accompanied, and the ultrasonic frequency is 30 KHz.
6. The method of recycling a sapphire substrate according to claim 1, wherein: the high-temperature baking temperature in the step 2) and the step 4) is 950-fold-flow 1100 ℃, the pressure of the cavity of the high-temperature furnace is 0-1000mbar, the cavity is alternately pumped under the low pressure of 0-200mbar during the high-temperature section baking, the nitrogen flow in the baking process is 1000-fold-flow 5000sccm, the hydrogen flow is 50-500sccm, and the high-temperature baking time is kept for 2-7 h.
7. The method of recycling a sapphire substrate according to claim 1, wherein: the SPM acid-base cleaning process conditions in the step 6) and the step 8) are the same, and the used acid-base is concentrated in massH with a degree of 98%2SO4And H2O2The mixture solution of (A) and (B) is H2SO4:H2O2The temperature of the SPM mixed solution for cleaning the sample is 70-90 ℃ and the cleaning time is 3-10min, which is 3: 1.
8. The method of recycling a sapphire substrate according to claim 1, wherein: in the step 7), phosphoric acid liquor is used for etching, the liquor is formed by mixing 85% phosphoric acid and 98% sulfuric acid by weight, and the mixture ratio is H3PO4:H2SO4The etching temperature is 100-.
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