CN109888065A - A method of graphical sapphire substrate is made using heating laser stripping means - Google Patents
A method of graphical sapphire substrate is made using heating laser stripping means Download PDFInfo
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Abstract
The embodiment of the invention discloses a kind of methods using heating laser stripping means production graphical sapphire substrate, including carrying out laser scanning to the LED epitaxial wafer scrapped using heating laser peel-off device, it is put into high temperature furnace and carries out pyrolytic, mixed gas is one of hydrogen, nitrogen, chlorine, hydrogen chloride and two or more in high temperature furnace, total gas flow rate 5-100L/min, 600-1300 DEG C of temperature；It is placed in the aqueous slkali that temperature is 70-130 DEG C and stands, then be placed in the acid solution that temperature is 80-180 DEG C and stand；It is cleaned in the quartz cell of the mixed liquor of sulfuric acid and hydrogen peroxide that the volume ratio for having temperature to be 90-140 DEG C inside again is 1:4-7, is dried after being rinsed with deionized water.The epitaxial layer that the present invention removes the LED epitaxial wafer scrapped on graphical sapphire substrate on the basis of not damaging figure is fabricated to new graphical sapphire substrate, makes its re-using, simple process and low cost.
Description
Technical field
The invention belongs to photoelectron material manufacture technology fields, are related to a kind of utilization heating laser stripping means production figure
Change the method for Sapphire Substrate.
Background technique
In light emitting diode (Light Emitting Diode) and the manufacturing process of other opto-electronic devices, sapphire
Substrate using increasingly extensive, be generally divided into plain film Sapphire Substrate and graphical sapphire substrate (Pattern
Sapphire Substrate:PSS).Wherein, graphical sapphire substrate is that many are processed in plain film Sapphire Substrate
With certain shapes and size micron dimension figure and be made, it can significantly improve the crystalline substance of Light-Emitting Diode epitaxial layer
Weight can form a kind of scatter with reflecting effect in light emitting diode substrate face and increase the extraction efficiency of light, and then significantly mention
The performance of high light emitting diode chip, therefore, patterned sapphire substrate is applied to LED epitaxial more and more widely
The growth course of piece.
In the growth course of LED epitaxial slice, it can usually generate and scrap piece, Fig. 1 is the LED epitaxial wafer scrapped
Structural schematic diagram need the epitaxial layer for the LED epitaxial wafer for scrapping these to get rid of to reduce production cost, can be recycled
Image conversion Sapphire Substrate is to re-use.There are many kinds of existing Sapphire Substrate recovery methods, the first is using machinery
Grinding is that the epitaxial layer in Sapphire Substrate is removed the left side 30um by mechanical lapping to remove the epitaxial layer in Sapphire Substrate
Right thickness, is typically used in the recycling of plain film Sapphire Substrate, if applied on recycling graphical sapphire substrate,
Grinding shallowly will not all remove epitaxial layer, if it is desired to all removal must grind relatively deep, and that grinds relatively deep can destroy indigo plant
Figure on jewel substrate can not restore original pattern topology, so mechanical grinding method is unfavorable for graphic sapphire lining
The recycling at bottom causes graphical sapphire substrate that cannot be recycled, and drop the cost for manufacturing LED epitaxial wafer can not
It is low.Second is to utilize the epitaxial layer on plasma etching method removal graphical sapphire substrate, still, plasma etching
Etching gas used in method also will cause to damage to the figure on graphical sapphire substrate, so that graphic sapphire
Substrate can not restore original appearance.The third is simple utilization pyrolysis method, is enough to decompose gallium nitride at high temperature, but point
Gallium can be precipitated in solution preocess and be gathered into gallium ball, gallium ball can assemble higher heat at high temperature, cause damaged graphics.In short, existing
The epitaxial layer on graphical sapphire substrate is removed on the basis of not damaging figure in a kind of no effective method.
Summary of the invention
The object of the invention is to solve the above-mentioned problems in the prior art, a kind of utilization heating laser removing is provided
The method that method makes graphical sapphire substrate, this method can be by the LED epitaxial wafer scrapped on the basis of not damaging figure
Epitaxial layer on removal graphical sapphire substrate is fabricated to new graphical sapphire substrate, makes its re-using, to drop
The production cost of low LED epitaxial wafer.
To achieve the above object, the technical solution of the invention is as follows: a kind of to utilize heating laser stripping means production figure
The method of shape Sapphire Substrate, comprising the following steps: sample is the LED epitaxial wafer scrapped；
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 80-250uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 5-15W to sample from indigo plant
Jewel side is entirely scanned, and is made when scanning in the case where guaranteeing that graphical sapphire substrate is not damaged graphical blue precious
Stone lining bottom and the interface of epitaxial layer are formed loosely；
The heating laser peel-off device includes laser lift-off apparatus body, and the laser lift-off apparatus body includes being set to
The mobile platform of lower end, the mobile platform are provided with heated base, and sample stage, the heating are provided on the heated base
Pedestal includes the electric heater unit being set to below the sample stage and for heating to the sample stage, the sample stage lower end
It is additionally provided with the temperature sensor for test sample platform temperature, is covered with insulation cover above the sample stage, the insulation cover
The heat-insulation transparent window for facilitating laser to pass through is provided on position corresponding to top and the sample stage；The laser lift-off equipment
Ontology includes solid state laser, beam shaping mirror, beam expanding lens, galvanometer motor, galvanometer eyeglass, field lens and NI Vision Builder for Automated Inspection, is gone back
It is located at below the solid state laser including industrial PC and control software, the beam shaping mirror, the beam expanding lens, galvanometer mirror
Piece, galvanometer motor and field lens, beam shaping mirror are located at after the solid state laser, the laser that the solid state laser is issued
Beam shaping, the galvanometer motor are located at before field lens, and the movement of the galvanometer eyeglass is controlled according to the instruction that control software issues, from
And realize different scan path and cutting path, the mobile platform is located at below the solid state laser, and the control is soft
Part is run on the industrial PC；
B, the sample after laser scanning is put into high temperature furnace and carries out pyrolytic；The high temperature furnace be high-temperature annealing furnace,
Bake furnace or alloying furnace；
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen for being evacuated to after vacuum in high temperature furnace, pressure
It is maintained at -0.1~-0.5Mpa；
(2) it is passed through mixed gas, total gas flow rate 5-100L/min, until 600-1300 DEG C of temperature, high temperature hold time 5-
60min starts to be naturally cooling to room temperature, and the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is hydrogen
One of gas, nitrogen, chlorine, hydrogen chloride and two or more mixed gas；
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 5- in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 70-130 DEG C
30min is tentatively corroded the residuals on the sample after pyrolytic；The aqueous slkali is that concentration is 20%-70%'s
The potassium hydroxide KaOH solution that sodium hydroxide NaOH or concentration are 20%-70%；
(2) sample after alkaline solution treatment is placed in again quiet in the acid solution in the anticorrosion vessel for being 80-180 DEG C equipped with temperature
5-30min is set, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 65%-68%；
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
The hydrogen peroxide of 90-140 DEG C of 96% sulfuric acid and 30-32% according to volume ratio 1:4-7 mixed liquor, after cleaning 5-20min, by sample
Product dry after being rinsed with deionized water, obtain graphical sapphire substrate.
Further preferably, the lower end of the insulation cover is connected and fixed in the groove of the heated base upper end,
Cavity is provided in the inner wall of side, winding is provided with cooling water-circulating pipe in the cavity, wherein the cooling water circulation pipe
Inlet and outlet are located on the outer wall of the insulation cover.
It is further preferred that the temperature sensor is thermocouple；The electric heater unit is electric heating wire or electric heating
Piece or electric heating lamp；The temperature sensor and electric heater unit are connect with engineering computer respectively.
It is further preferred that the electric heater unit is used to the sample stage being heated to 800-1200 in 3-5min
DEG C, such as 900 DEG C or 1000 DEG C.
It is further preferred that the height of the heating cavity constituted between the insulation cover and heated base is 300-500mm,
It is preferred that 300-400mm.
It is further preferred that the transparency window is the heatproof lens or heat-protecting glass for not absorbing laser.
It is further preferred that the step B(2) in, the total gas flow rate 10-40L/min.
It is further preferred that the step B(2) in, the high temperature hold time 10-40min.
It is further preferred that the step B(2) in, when mixed gas is hydrogen, nitrogen, chlorine, two in hydrogen chloride
When kind, mixed gas flow ratio is 1:0.3-30；Preferably 1:3-8.
It is further preferred that the step C(1) in, the temperature of aqueous slkali is 90-110 DEG C in the anticorrosion vessel；
The concentration of sodium hydroxide NaOH solution is 30%-60%；The concentration of potassium hydroxide KaOH solution is 30%-60%.
It is further preferred that it is 10-15min that sample carries out scavenging period in quartz cell in the step D；Sulfuric acid
Volume ratio with hydrogen peroxide is 1:5-6.
The beneficial effects of the present invention are: the LED epitaxial wafer scrapped is scanned by heating laser peel-off device, laser is used
Lift-off technology keeps graphical sapphire substrate and the epitaxial layer at epitaxial layer contact interface loose；Due to the forbidden band of epitaxial layer GaN
Width is 3.4eV, the energy of a light beam between GaN and sapphire forbidden bandwidth (EgGan < Eglaser <
Egsapphire), the energy if optical maser wavelength is 355nm scans entire sample from sapphire side, then this Shu Jiguang will not be by
Sapphire is absorbed, but can be absorbed by the GaN at interface, GaN and graphic sapphire contact layer can be become loose.Pass through again
Pyrolysis method decomposes the GaN of epitaxial layer completely, and because the temperature of the pyrolysis method is low, the time is short, so will not be right
The figure of graphical sapphire substrate causes to damage.Then the remaining object of substrate surface is removed by the method for acid, caustic corrosion again
Matter and dirty, the acid used, aqueous slkali do not serve as a contrast graphic sapphire by control temperature, concentration, time corrosion residues
There is corrosion phenomenon at bottom, so having obtained undamaged graphical sapphire substrate and having been re-used, greatly improves figure
The utilization rate for changing Sapphire Substrate, thereby reduces LED production cost.In addition, the method simple process, qualification rate is up to arrived
95% or more, recovery time is short.
Since graphical sapphire substrate and GaN epitaxial layer are dissimilar materials, the lattice constant and thermal expansion of the two
There are a great differences for coefficient, and the lattice constant mismatch degree between GaN and Sapphire Substrate is more than 14%, and thermal mismatching degree differs one times
More, lattice mismatch and differential thermal expansion big in this way will necessarily cause the remaining for growing GaN epitaxy piece on a sapphire substrate
Stress problem, when removing, are easy to break, and sample stage when being given by heating device using laser lift-off GaN epitaxial layer provides suitable
Temperature environment (be heated to 800-1000 DEG C in 3-5min, can guarantee to greatest extent peeling effect at this temperature while avoid
Influence to the translucency of heat-insulation transparent window), it reduces since there are a great differences for the lattice constant and thermal expansion coefficient of the two
Cause the lattice constant thermal mismatching between GaN and Sapphire Substrate to spend high problem, while passing through insulation cover for sample stage cover
Firmly, it is at a closed heating cavity, guarantees peeling effect, further decreases risk easy to break when removing, chamber
Body height is the preferred 300-400mm of 300-500mm(), height too self raising flour dirt window easy to pollute is avoided, while avoiding due to height
It is too low that lens is caused to cause light transmittance to change even fragmentation due to heat radiation denaturation；Heat-insulation transparent window can facilitate laser pass through and
It does not absorb laser, laser energy free of losses, and its thermal insulation well laser head can be effectively protected and avoid laser head excessively high
Heat under damage.
Recycling graphical sapphire substrate is carried out to the LED epitaxial wafer scrapped using plasma etching method, recycling is closed
Lattice rate 40% hereinafter, recovery time is long, the figure Light deformation of the graphical sapphire substrate of recycling, as shown in Figure 6.Utilize list
One pyrolysis method carries out recycling graphical sapphire substrate to the LED epitaxial wafer scrapped, recycling qualification rate 50% with
Under, recovery time is short, and the damaged graphics of the graphical sapphire substrate of recycling, flash is more, as shown in Figure 7.Using of the invention
Method carries out recycling graphical sapphire substrate to the LED epitaxial wafer scrapped, and recycling qualification rate is 95% or more, recovery time
Short, the figure of the graphical sapphire substrate of recycling is complete, without any damage, as shown in Figure 8.So only using this hair
The graphical sapphire substrate of bright method recycling can recycle, and others recycle effect poor, and yield rate is low.
In conclusion the LED epitaxial wafer scrapped can be removed figure by method of the invention on the basis of not damaging figure
The epitaxial layer changed in Sapphire Substrate is fabricated to new graphical sapphire substrate, makes its re-using, to reduce LED extension
The production cost of piece.This method simple process and low cost, while being also suitble to the recycling again of large-size sapphire substrate, tool
There is extraordinary application prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the LED epitaxial wafer scrapped；
Fig. 2 is the structural schematic diagram of the laser lift-off machine LED epitaxial wafer that treated scraps of the invention；
Fig. 3 is the structural representation of the LED epitaxial wafer scrapped after the present invention is decomposed epitaxial layer using pyrolytic technology completely
Figure；
Fig. 4 is that the present invention utilizes acid, the structural schematic diagram of the caustic corrosion method LED epitaxial wafer that treated scraps；
Fig. 5 is the structural schematic diagram of present invention graphical sapphire substrate after the recovery；
Fig. 6 is the photo of the figure of the graphical sapphire substrate recycled using plasma etching method；
Fig. 7 is the photo using the figure of the graphical sapphire substrate of single pyrolysis method recycling；
Fig. 8 is the photo of the figure of the graphical sapphire substrate recycled using the method for the present invention.
In figure: 1 is graphical sapphire substrate；2 be GaN epitaxial layer.
Fig. 9 is the structural schematic diagram of the heating device in the present invention on the mobile platform of heating laser peel-off device；
Figure 10 is the schematic diagram of cooling water-circulating pipe in heating laser peel-off device in the present invention.
In figure, 11 be heated base；12 be electric heater unit；3 be sample stage；4 be thermocouple；5 be protective cover；6 for every
Thermal lens；7 be water inlet；8 be water outlet；9 be cooling water-circulating pipe；10 be mobile platform.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the invention will be further described.
Fig. 1 is the structural schematic diagram for the LED epitaxial wafer scrapped, and 1 is graphical sapphire substrate, 2 is GaN epitaxial layer；It is right
In the LED epitaxial layer grown on graphical sapphire substrate mainly include N-type layer, multiple quantum well layer and P-type layer, in the market
Comparative maturity, so not specifically indicating that the specific structure of epitaxial layer in Fig. 1.
Embodiment 1, a method of Sapphire Substrate is prepared using heating laser peel-off device, comprising the following steps: sample
Product are the LED epitaxial wafer scrapped.
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 80uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 5W to sample from sapphire side
Entirely scanned, make when scanning in the case where guaranteeing that graphical sapphire substrate is not damaged graphical sapphire substrate and
The interface of epitaxial layer is formed loosely.The structure of LED epitaxial wafer after treatment is as shown in Fig. 2, 1 serves as a contrast for graphic sapphire
Bottom, 2 are GaN epitaxial layer.
As shown in figure 9, the heating laser peel-off device includes laser lift-off apparatus body, the laser lift-off equipment
Ontology includes the mobile platform 10 for being set to lower end, and the mobile platform 10 is provided with heated base 11, the heated base 11
On be provided with sample stage, the heated base 11 includes being set to 3 lower section of sample stage and for giving the sample stage 3 heating
Electric heater unit, 3 lower end of sample stage is additionally provided with the temperature sensor for 3 temperature of test sample: thermocouple 4, institute
It states and is covered with insulation cover 5 above sample stage 3, the side of being provided on position corresponding to the top of the insulation cover 5 and the sample stage 3
Just the heat-insulation transparent window that laser passes through: heat-insulated 6(can also be heat-protecting glass).The laser lift-off apparatus body includes that solid swashs
Light device, beam shaping mirror, beam expanding lens, galvanometer motor, galvanometer eyeglass, field lens and NI Vision Builder for Automated Inspection, further include industrial PC and
Control software, the beam shaping mirror is located at below the solid state laser, the beam expanding lens, galvanometer eyeglass, galvanometer motor and
Field lens, beam shaping mirror are located at after the solid state laser, the laser beam reshaping that the solid state laser is issued, the vibration
Mirror motor is located at before field lens, the movement of the galvanometer eyeglass is controlled according to the instruction that control software issues, to realize different
Scan path and cutting path, the mobile platform 10 are located at below the solid state laser, and the control software runs on institute
It states on industrial PC.
In the present embodiment, the lower end of the insulation cover 6 is connected and fixed in the groove 101 of 11 upper end of heated base.
As shown in Figure 10, cavity is provided in the side inner wall of the insulation cover 5, winding is provided with cooling water-circulating pipe in the cavity
9, wherein the water inlet 7 and water outlet 8 of the cooling water circulation pipe 9 are located on the outer wall of the insulation cover 5.The electricity adds
Thermal 12 is electric heating wire or electric heating sheets, such as nichrome point heater strip.The thermocouple 4 and electric heater unit 12 are distinguished
It is connect with engineering computer, engineering computer is used for the working condition of the feedback control electric heater unit 12 according to thermocouple 4.The electricity
Heating device 12 is used to the sample stage being heated to 600-1500 DEG C, preferably 800-1200 DEG C in 3-5min, such as 800 DEG C,
900 DEG C, 1000 DEG C etc..The control circuit being related to is ordinary skill in the art means, not excessive herein to repeat.
In use, then covering upper protective cover 5 by being placed on sample stage 3 in the Sapphire Substrate for growing GaN material, opening
Dynamic electric heater unit 2, to be heated to set temperature, thermocouple feedback signal gives engineering computer, and control electric heater unit stops adding
Then with by laser head the Sapphire Substrate that the scanning irradiation of laser light heatproof lens 6 grows GaN material occurs for heat, to reach
To the purpose of peeling GaN epitaxial wafer.It is located at suitable temperature environment when due to GaN epitaxy piece, avoids due to GaN material and indigo plant
There are a great differences, and lattice constant thermal mismatching between the two to be caused to be spent for the lattice constant and thermal expansion coefficient of jewel substrate
High problem.And heatproof lens 6 can facilitate laser to pass through and laser head is effectively protected, and avoid laser head in excessively high heat
The lower damage of amount.The heating laser peel-off device peeling effect is good, does not occur fragmentation phenomenon, and peeling effect is stablized.
B, the sample after laser scanning is put into high-temperature annealing furnace and carries out pyrolytic.
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen after vacuum being evacuated in high temperature furnace,
Pressure is maintained at -0.5Mpa；
(2) it is passed through mixed gas, total gas flow rate 100L/min, until 600 DEG C of temperature, high temperature hold time 60min, start nature
It is cooled to room temperature, the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas be hydrogen, nitrogen, chlorine,
One of hydrogen chloride or flow proportional are the hydrogen of 1:3 and the mixed gas of nitrogen.
The structure of LED epitaxial wafer after treatment is as shown in figure 3,1 is graphical sapphire substrate.
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 30min in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 130 DEG C, it will
The residuals on sample after pyrolytic are tentatively corroded；The aqueous slkali is the sodium hydroxide NaOH that concentration is 20%
Or the potassium hydroxide KaOH solution that concentration is 20%.
(2) sample after alkaline solution treatment is placed in the acid solution in the anticorrosion vessel for being 180 DEG C equipped with temperature again
5min is stood, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 65%.
The structure of LED epitaxial wafer after treatment is as shown in figure 4,1 is graphical sapphire substrate.
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
90 DEG C of 96% sulfuric acid and 30% hydrogen peroxide according to volume ratio 1:4 mixed liquor, after cleaning 20min, by sample deionization
Water dries after rinsing, and obtains graphical sapphire substrate, as shown in figure 5,1 is graphical sapphire substrate.
The LED epitaxial wafer recycling qualification rate of embodiment 1 scrapped reaches 98% or more, the graphical sapphire substrate of recycling
Figure there is no any damage, and it is short to recycle the process-cycle.
Embodiment 2, a method of Sapphire Substrate is prepared using heating laser peel-off device, comprising the following steps: sample
Product are the LED epitaxial wafer scrapped.
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 100uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 7W to sample from sapphire one
Side is entirely scanned, and makes graphical sapphire substrate in the case where guaranteeing that graphical sapphire substrate is not damaged when scanning
It is formed loosely with the interface of epitaxial layer.The structure of LED epitaxial wafer after treatment is as shown in Fig. 2, 1 serves as a contrast for graphic sapphire
Bottom, 2 are GaN epitaxial layer.The heating laser peel-off device is the same as embodiment 1.
B, the sample after laser scanning is put into high-temperature annealing furnace and carries out pyrolytic.
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen after vacuum being evacuated in high temperature furnace,
Pressure is maintained at -0.1Mpa；
(2) it is passed through mixed gas, total gas flow rate 5L/min, until 900 DEG C of temperature, high temperature hold time 20min, start nature drop
It warms to room temperature, the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is the hydrogen that flow proportional is 1:30
The mixed gas or hydrogen of gas and chlorine, nitrogen, chlorine, three kinds of mixed gas in hydrogen chloride.
The structure of LED epitaxial wafer after treatment is as shown in figure 3,1 is graphical sapphire substrate.
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 25min in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 70 DEG C, it will be high
The residuals on sample after temperature decomposition are tentatively corroded；The aqueous slkali be the sodium hydroxide NaOH that concentration is 70% or
The potassium hydroxide KaOH solution that concentration is 70%.
(2) sample after alkaline solution treatment is placed in again quiet in the acid solution in the anticorrosion vessel for being 80 DEG C equipped with temperature
30min is set, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 68%.
The structure of LED epitaxial wafer after treatment is as shown in figure 4,1 is graphical sapphire substrate.
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
140 DEG C of 96% sulfuric acid and 31% hydrogen peroxide according to volume ratio 1:7 mixed liquor, after cleaning 5min, by sample deionization
Water dries after rinsing, and obtains graphical sapphire substrate, as shown in figure 5,1 is graphical sapphire substrate.
The LED epitaxial wafer recycling qualification rate of embodiment 2 scrapped reaches 98% or more, the graphical sapphire substrate of recycling
Figure there is no any damage, and it is short to recycle the process-cycle.
Embodiment 3, a method of Sapphire Substrate is prepared using heating laser peel-off device, comprising the following steps: sample
Product are the LED epitaxial wafer scrapped.
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 225uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 13W to sample from sapphire one
Side is entirely scanned, and makes graphical sapphire substrate in the case where guaranteeing that graphical sapphire substrate is not damaged when scanning
It is formed loosely with the interface of epitaxial layer.The structure of LED epitaxial wafer after treatment is as shown in Fig. 2, 1 serves as a contrast for graphic sapphire
Bottom, 2 are GaN epitaxial layer.The heating laser peel-off device is the same as embodiment 1.
B, the sample after laser scanning is put into high-temperature annealing furnace and carries out pyrolytic.
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen after vacuum being evacuated in high temperature furnace,
Pressure is maintained at -0.2Mpa；
(2) it is passed through mixed gas, total gas flow rate 40L/min, until 1000 DEG C of temperature, high temperature hold time 10min, start nature
It is cooled to room temperature, the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is that flow proportional is 1:0.3
Hydrogen and hydrogen chloride four kinds of mixed gas or hydrogen, nitrogen, chlorine and hydrogen chloride mixed gas.
The structure of LED epitaxial wafer after treatment is as shown in figure 3,1 is graphical sapphire substrate.
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 20min in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 100 DEG C, it will
The residuals on sample after pyrolytic are tentatively corroded；The aqueous slkali is the sodium hydroxide NaOH that concentration is 60%
Or the potassium hydroxide KaOH solution that concentration is 60%.
(2) sample after alkaline solution treatment is placed in the acid solution in the anticorrosion vessel for being 120 DEG C equipped with temperature again
12min is stood, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 66%.By
The structure for LED epitaxial wafer that treated is as shown in figure 4,1 is graphical sapphire substrate.
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
120 DEG C 96% of sulfuric acid and 32% hydrogen peroxide according to volume ratio 1:6 mixed liquor, clean 15min after, by sample deionized water
It is dried after flushing, obtains graphical sapphire substrate, as shown in figure 5,1 is graphical sapphire substrate.
The LED epitaxial wafer recycling qualification rate of embodiment 3 scrapped reaches 98% or more, the graphical sapphire substrate of recycling
Figure there is no any damage, and it is short to recycle the process-cycle.
Embodiment 4, a method of Sapphire Substrate is prepared using heating laser peel-off device, comprising the following steps: sample
Product are the LED epitaxial wafer scrapped.
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 240uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 15W to sample from sapphire one
Side is entirely scanned, and makes graphical sapphire substrate in the case where guaranteeing that graphical sapphire substrate is not damaged when scanning
It is formed loosely with the interface of epitaxial layer.The structure of LED epitaxial wafer after treatment is as shown in Fig. 2, 1 serves as a contrast for graphic sapphire
Bottom, 2 are GaN epitaxial layer.The heating laser peel-off device is the same as embodiment 1.
B, the sample after laser scanning is put into high-temperature annealing furnace and carries out pyrolytic.
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen after vacuum being evacuated in high temperature furnace,
Pressure is maintained at -0.3Mpa；
(2) it is passed through mixed gas, total gas flow rate 25L/min, until 1200 DEG C of temperature, high temperature hold time 40min, start nature
It is cooled to room temperature, the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is that flow proportional is 1:8's
The mixed gas or nitrogen and four kinds of mixed gas of hydrogen chloride of nitrogen and chlorine.
The structure of LED epitaxial wafer after treatment is as shown in figure 3,1 is graphical sapphire substrate.
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 15min in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 105 DEG C, it will
The residuals on sample after pyrolytic are tentatively corroded；The aqueous slkali is the sodium hydroxide NaOH that concentration is 50%
Or the potassium hydroxide KaOH solution that concentration is 50%.
(2) sample after alkaline solution treatment is placed in the acid solution in the anticorrosion vessel for being 100 DEG C equipped with temperature again
25min is stood, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 67%.By
The structure for LED epitaxial wafer that treated is as shown in figure 4,1 is graphical sapphire substrate.
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
130 DEG C of 96% sulfuric acid and 31.5% hydrogen peroxide according to volume ratio 1:5 mixed liquor, after cleaning 10min, by sample spend from
Sub- water dries after rinsing, and obtains graphical sapphire substrate, as shown in figure 5,1 is graphical sapphire substrate.
The LED epitaxial wafer recycling qualification rate of embodiment 4 scrapped reaches 98% or more, the graphical sapphire substrate of recycling
Figure there is no any damage, and it is short to recycle the process-cycle.
Embodiment 5, a method of Sapphire Substrate is prepared using heating laser peel-off device, comprising the following steps: sample
Product are the LED epitaxial wafer scrapped.
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 250uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 10W to sample from sapphire one
Side is entirely scanned, and makes graphical sapphire substrate in the case where guaranteeing that graphical sapphire substrate is not damaged when scanning
It is formed loosely with the interface of epitaxial layer.The structure of LED epitaxial wafer after treatment is as shown in Fig. 2, 1 serves as a contrast for graphic sapphire
Bottom, 2 are GaN epitaxial layer.The heating laser peel-off device is the same as embodiment 1.
B, the sample after laser scanning is put into high-temperature annealing furnace and carries out pyrolytic.
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen after vacuum being evacuated in high temperature furnace,
Pressure is maintained at -0.4Mpa；
(2) it is passed through mixed gas, total gas flow rate 10L/min, until 1300 DEG C of temperature, high temperature hold time 5min, start nature
It is cooled to room temperature, the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is that flow proportional is 1:5's
The mixed gas of chlorine and hydrogen chloride.
The structure of LED epitaxial wafer after treatment is as shown in figure 3,1 is graphical sapphire substrate.
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 5min in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 120 DEG C, it will be high
The residuals on sample after temperature decomposition are tentatively corroded；The aqueous slkali be the sodium hydroxide NaOH that concentration is 30% or
The potassium hydroxide KaOH solution that concentration is 30%.
(2) sample after alkaline solution treatment is placed in the acid solution in the anticorrosion vessel for being 150 DEG C equipped with temperature again
20min is stood, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 68%.By
The structure for LED epitaxial wafer that treated is as shown in figure 4,1 is graphical sapphire substrate.
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
110 DEG C of 96% sulfuric acid and 30.5% hydrogen peroxide spend sample after cleaning 13min according to the mixed liquor of volume ratio 1:5.5
Ionized water dries after rinsing, and obtains graphical sapphire substrate, as shown in figure 5,1 is graphical sapphire substrate.
The LED epitaxial wafer recycling qualification rate of embodiment 5 scrapped reaches 98% or more, the graphical sapphire substrate of recycling
Figure there is no any damage, and it is short to recycle the process-cycle.
Above-described embodiment be only it is preferred and illustrative, those skilled in the art can do according to the description of this patent
Change with technology, is all covered by the protection scope of this patent.
Claims (10)
1. a kind of method using heating laser stripping means production graphical sapphire substrate, it is characterised in that: including following
Step: sample is the LED epitaxial wafer scrapped；
A, laser scanning is carried out to sample using heating laser peel-off device；
Be 80-250uj with energy, heating laser peel-off device that wavelength 355nm, removing power are 5-15W to sample from indigo plant
Jewel side is entirely scanned, and is made when scanning in the case where guaranteeing that graphical sapphire substrate is not damaged graphical blue precious
Stone lining bottom and the interface of epitaxial layer are formed loosely；
The heating laser peel-off device includes laser lift-off apparatus body, and the laser lift-off apparatus body includes being set to
The mobile platform of lower end, the mobile platform are provided with heated base, and sample stage, the heating are provided on the heated base
Pedestal includes the electric heater unit being set to below the sample stage and for heating to the sample stage, the sample stage lower end
It is additionally provided with the temperature sensor for test sample platform temperature, is covered with insulation cover above the sample stage, the insulation cover
The heat-insulation transparent window for facilitating laser to pass through is provided on position corresponding to top and the sample stage；The laser lift-off equipment
Ontology includes solid state laser, beam shaping mirror, beam expanding lens, galvanometer motor, galvanometer eyeglass, field lens and NI Vision Builder for Automated Inspection, is gone back
It is located at below the solid state laser including industrial PC and control software, the beam shaping mirror, the beam expanding lens, galvanometer mirror
Piece, galvanometer motor and field lens, beam shaping mirror are located at after the solid state laser, the laser that the solid state laser is issued
Beam shaping, the galvanometer motor are located at before field lens, and the movement of the galvanometer eyeglass is controlled according to the instruction that control software issues, from
And realize different scan path and cutting path, the mobile platform is located at below the solid state laser, and the control is soft
Part is run on the industrial PC；
B, the sample after laser scanning is put into high temperature furnace and carries out pyrolytic；The high temperature furnace be high-temperature annealing furnace,
Bake furnace or alloying furnace；
(1) sample after laser scanning is placed in high temperature furnace；Heating, is filled with nitrogen for being evacuated to after vacuum in high temperature furnace, pressure
It is maintained at -0.1~-0.5Mpa；
(2) it is passed through mixed gas, total gas flow rate 5-100L/min, until 600-1300 DEG C of temperature, high temperature hold time 5-
60min starts to be naturally cooling to room temperature, and the GaN for the sample for keeping interface loose is sufficiently decomposed；The mixed gas is hydrogen
One of gas, nitrogen, chlorine, hydrogen chloride and two or more mixed gas；
C, the sample after pyrolytic is subjected to wet etching and removes removal of residue；
(1) stand 5- in the aqueous slkali sample after pyrolytic being placed in the anticorrosion vessel that temperature is 70-130 DEG C
30min is tentatively corroded the residuals on the sample after pyrolytic；The aqueous slkali is that concentration is 20%-70%'s
The potassium hydroxide KaOH solution that sodium hydroxide NaOH or concentration are 20%-70%；
(2) sample after alkaline solution treatment is placed in again quiet in the acid solution in the anticorrosion vessel for being 80-180 DEG C equipped with temperature
5-30min is set, minor contaminants object remaining on sample is corroded clean；The acid solution is the phosphoric acid that concentration is 65%-68%；
D, the processed sample of wet etching is cleaned；
The processed sample of wet etching is placed in the not closed quartz cell of heating and is cleaned, there is the temperature to be in quartz cell
The hydrogen peroxide of 90-140 DEG C of 96% sulfuric acid and 30-32% according to volume ratio 1:4-7 mixed liquor, after cleaning 5-20min, by sample
Product dry after being rinsed with deionized water, obtain graphical sapphire substrate.
2. the method according to claim 1 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the lower end of the insulation cover is connected and fixed in the groove of the heated base upper end, is provided in the inner wall of side
Cavity, the interior winding of the cavity is provided with cooling water-circulating pipe, wherein the inlet and outlet of the cooling water circulation pipe point
It Wei Yu not be on the outer wall of the insulation cover.
3. the method according to claim 1 or 2 using heating laser stripping means production graphical sapphire substrate,
Be characterized in that: the temperature sensor is thermocouple；The electric heater unit is electric heating wire or electric heating sheets or electric heating lamp；
The temperature sensor and electric heater unit are connect with engineering computer respectively.
4. the method according to claim 3 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the electric heater unit is used to the sample stage being heated to 800-1200 DEG C in 3-5min.
5. the method according to claim 4 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the height of the heating cavity constituted between the insulation cover and heated base is 300-500mm；The transparency window is not
Absorb the heatproof lens or heat-protecting glass of laser.
6. the method according to claim 5 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the step B(2) in, when mixed gas is hydrogen, nitrogen, chlorine, two kinds in hydrogen chloride, mixed gas
Flow proportional is 1:0.3-30.
7. the method according to claim 6 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the step B(2) in, the total gas flow rate 10-40L/min.
8. the method according to claim 7 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the step B(2) in, the high temperature hold time 10-40min.
9. the method according to claim 8 using heating laser stripping means production graphical sapphire substrate, special
Sign is: the step C(1) in, the temperature of aqueous slkali is 90-110 DEG C in the anticorrosion vessel；Sodium hydroxide NaOH is molten
The concentration of liquid is 30%-60%；The concentration of potassium hydroxide KaOH solution is 30%-60%.
10. the method according to claim 9 using heating laser stripping means production graphical sapphire substrate, special
Sign is: in the step D, it is 10-15min that sample carries out scavenging period in quartz cell；The volume of sulfuric acid and hydrogen peroxide
Than for 1:5-6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113628960A (en) * | 2021-07-28 | 2021-11-09 | 山东大学 | High-temperature laser stripping device and method for GaN single crystal substrate on sapphire template |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113628960A (en) * | 2021-07-28 | 2021-11-09 | 山东大学 | High-temperature laser stripping device and method for GaN single crystal substrate on sapphire template |
| CN113628960B (en) * | 2021-07-28 | 2024-03-22 | 山东大学 | High-temperature laser stripping device and method for GaN single crystal substrate on sapphire template |
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