CN108807148B - Method for recovering sapphire patterned substrate for GaN-LED by combining physics and chemistry - Google Patents

Method for recovering sapphire patterned substrate for GaN-LED by combining physics and chemistry Download PDF

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CN108807148B
CN108807148B CN201810665067.5A CN201810665067A CN108807148B CN 108807148 B CN108807148 B CN 108807148B CN 201810665067 A CN201810665067 A CN 201810665067A CN 108807148 B CN108807148 B CN 108807148B
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CN108807148A (en
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马旺
王成新
肖成峰
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Shandong Inspur Huaguang Optoelectronics Co Ltd
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02032—Preparing bulk and homogeneous wafers by reclaiming or re-processing
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Abstract

A method for recovering a sapphire patterned substrate for a GaN-LED by combining physics and chemistry comprises the following stepsThe method comprises the following steps: a) baking the waste epitaxial wafer at high temperature; b) carrying out ultrasonic treatment in an acetone solution; c) performing ultrasonic treatment in ethanol solution for 10 min; d) cleaning in a mixed solution of sulfuric acid and hydrogen peroxide; e) ICP etching; f) carrying out ultrasonic treatment in an acetone solution; g sonication in ethanol solution. Removing the GaN layer by physical baking in a high temperature furnace without any damage to the sapphire substrate, cleaning the surface of the substrate by a wet method, etching by Inductively Coupled Plasma (ICP),
Figure DEST_PATH_IMAGE001
and
Figure 550878DEST_PATH_IMAGE002
the residual GaN impurities are removed by etching the mixed gas, the process method is simple, the substrate is not damaged, and the cost is saved. Because the GaN layer is removed by adopting a physical baking method, the substrate is not damaged, the process is simple, and the substrate is not easy to be polluted. And the substrate is cleaned by a wet method and ICP (inductively coupled plasma) and the residual GaN impurities are removed, so that the requirement of a new substrate is met and the cost is saved.

Description

Method for recovering sapphire patterned substrate for GaN-LED by combining physics and chemistry
Technical Field
The invention relates to the technical field of photoelectron manufacturing, in particular to a method for recovering a sapphire patterned substrate for a GaN-LED by combining physics and chemistry.
Background
In the field of semiconductor optoelectronics, epitaxial layers of GaN material are grown primarily on sapphire substrates, which have many advantages: firstly, the stability of sapphire is good; secondly, the sapphire substrate is mature in production and application, good in quality and capable of being applied to a high-temperature growth process; finally, sapphire is mechanically stiff and easy to handle and clean, so most GaN-LEDs are grown on sapphire substrates. However, the problem of surface light emission is the biggest problem of growing GaN materials on sapphire substrates, and although GaN-based LEDs are already industrialized, the problem of low light emission efficiency of chips is still not well solved. In terms of the light emitting properties of GaN-based LEDs, there are two main approaches generally used to improve the light emitting efficiency of GaN-based LEDs, one is to improve the internal quantum efficiency thereof, and the other is to improve the external quantum efficiency thereof. Because the GaN power type LED material generally adopts MOCVD epitaxial growth and a multi-quantum well structure, the improvement of the internal quantum efficiency is not obvious.
Research shows that the patterned Sapphire substrate, which is referred to as a pss (patterned Sapphire substrate) structure for short, enables the downward light propagation direction to be from an almost specified direction to any direction, and can effectively improve the light extraction efficiency of the LED. The PSS can solve the problem that the sapphire and the GaN have large lattice mismatch and thermal expansion coefficient mismatch, and meanwhile, the PSS micro-pattern structure changes the growth process of the GaN, can inhibit the extension of defects to an epitaxial surface and reduces the defect density of the epitaxy. On the other hand, the refractive index of the GaN and the sapphire substrate is different from that of air, the refractive index (2.4) of the GaN material is higher than that (1.7) of the sapphire substrate and that (1.0) of the air, the PSS graph structure changes the transmission route of light emitted by the active region, the light emitted by the active region is incident on the PSS graph and reflected back, and is incident on the interface of the GaN and the air through the GaN material, and compared with the common sapphire plane, the incident angle is reduced, the chance of total reflection is reduced, and the light emergent chance is increased; therefore, most of GaN-LEDs grown in the industry at present adopt PSS, MOCVD grows GaN-LEDs on sapphire patterned substrates, abnormal epitaxial wafers are often generated in the growth process due to fluctuation of hardware and growth, the requirement of die preparation can be met, the epitaxial wafers do not have process removal and can only be treated as waste wafers finally, the waste wafers are accumulated more and more in the past, and material waste is caused.
201110217923.9 the present invention relates to a method for manufacturing a vertical structure light emitting diode by wet stripping a GaN-based epitaxial layer and a sapphire substrate, comprising the steps of: a) preparing a patterned growth substrate, wherein the growth substrate sequentially comprises a sapphire substrate, a second layer of high-melting-point material easy to corrode and a first layer of high-melting-point material with stability from bottom to top, and the melting points of the second layer of high-melting-point material and the first layer of high-melting-point material are both higher than 900 ℃; b) growing a GaN-based light emitting diode epitaxial layer on the patterned growth substrate, wherein the GaN-based light emitting diode epitaxial layer sequentially comprises N-type GaN and P-type GaN from bottom to top; c) sequentially forming a transparent conductive film, an omnibearing reflecting layer, a conductive reflecting layer and a passivated metal protective layer on the GaN-based light emitting diode epitaxial layer from bottom to top, wherein the conductive reflecting layer is connected with the transparent conductive film through a hole in the omnibearing reflecting layer, a supporting substrate with high thermal conductivity is bound to the passivated metal protective layer through a binding technology, part of the GaN-based epitaxial layer in the growth substrate is removed through a wet method, and the sapphire substrate is stripped; d) and removing the first layer of stable high-melting-point material in the growth substrate by dry etching to expose the N-type GaN, and preparing an N electrode on the N-type GaN.
The stripping sapphire substrate stated in the patent is to remove GaN by a wet method, but the precondition is that a layer of high-melting-point material easy to corrode and a first layer of high-melting-point material with stability grow in the growing process, then the GaN is stripped by the wet method, and then the first layer of high-melting-point material with stability in the growing substrate is removed by dry etching to achieve the stripping of the sapphire substrate and the GaN.
Disclosure of Invention
In order to overcome the defects of the technology, the invention provides a method for recovering a sapphire patterned substrate for a GaN-LED by combining physical and chemical methods, which can recover the sapphire patterned substrate from a waste epitaxial wafer.
The technical scheme adopted by the invention for overcoming the technical problems is as follows:
a method for recovering a sapphire patterned substrate for a GaN-LED by combining physics and chemistry comprises the following steps:
a) baking the waste epitaxial wafer in a high-temperature furnace at the high temperature of 1000-2000 ℃ for 3-6 hours;
b) taking out the baked epitaxial wafer from the high-temperature furnace, and putting the epitaxial wafer into an acetone solution for ultrasonic treatment for 10 min;
c) rinsing the treated epitaxial wafer with pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min;
d) placing the epitaxial wafer into a mixed solution of sulfuric acid and hydrogen peroxide with a volume ratio of 1:1-1:3, cleaning for 20min, and then washing with pure water;
e) BCl using inductively coupled plasma etcher3With Cl2Etching the epitaxial wafer for 10-30S in the mixed gas environment;
f) carrying out ultrasonic treatment on the etched epitaxial wafer in an acetone solution for 10min, and then washing the epitaxial wafer by using pure water;
g) and (4) rinsing the treated epitaxial wafer by using pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min.
Further, the temperature of the high temperature furnace in the step a) is 1500 ℃, and the baking time is 3 hours.
Further, the volume ratio of the sulfuric acid to the hydrogen peroxide in the step d) is 1: 2.
Further, the etching time in step e) is 10S.
The invention has the beneficial effects that: the method of the invention is that an epitaxial layer directly grows on a sapphire pattern substrate without growing a layer of high-melting-point material easy to corrode and a first layer of high-melting-point material with stability, so that the epitaxial growth is simplified, a GaN layer is removed by adopting a physical baking method of a high-temperature furnace without any damage to the sapphire substrate, then the surface of the substrate is cleaned by a wet method, and then inductively coupled plasma etching (ICP), BCl3With Cl2The residual GaN impurities are removed by etching the mixed gas, the process method is simple, the substrate is not damaged, and the cost is saved. Because the GaN layer is removed by adopting a physical baking method, the substrate is not damaged, the process is simple, and the substrate is not easy to be polluted. And the substrate is cleaned by a wet method and ICP (inductively coupled plasma) and the residual GaN impurities are removed, so that the requirement of a new substrate is met and the cost is saved.
Drawings
FIG. 1 is a schematic view of an epitaxial wafer according to the present invention;
FIG. 2 is a schematic view of a sapphire substrate with a few GaN impurities after the epitaxial layer GaN is removed according to the present invention;
FIG. 3 is a schematic view of a sapphire substrate with GaN impurities removed according to the present invention;
FIG. 4 is a photomicrograph of a new sapphire patterned substrate;
FIG. 5 is a photomicrograph of a sapphire patterned substrate treated by the method of the present invention;
in the figure, 1.GaN layer 2. sapphire pattern substrate 3.GaN impurity.
Detailed Description
The invention will be further described with reference to fig. 1 to 5.
A method for recovering a sapphire patterned substrate for a GaN-LED by combining physics and chemistry comprises the following steps:
a) the waste epitaxial wafer shown in the attached figure 1 is baked in a high temperature furnace at the temperature of 1000-2000 ℃ for 3-6 hours, and when the waste epitaxial wafer is baked at the high temperature, the GaN layer 1 of the waste epitaxial wafer volatilizes in the high temperature baking process, so that the epitaxial wafer can be restored to the original structure of the sapphire patterned substrate 2.
b) And taking the baked epitaxial wafer out of the high-temperature furnace, and putting the baked epitaxial wafer into an acetone solution for ultrasonic treatment for 10 min.
c) And (4) rinsing the treated epitaxial wafer by using pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min.
The epitaxial wafer taken out at this time had many GaN impurities on the surface of the sapphire patterned substrate 2 as shown in fig. 2. The cleaning by acetone and ethanol can achieve the purpose of removing oil stains and other impurities generated in the high-temperature baking process.
d) And (3) placing the epitaxial wafer into a mixed solution of sulfuric acid and hydrogen peroxide with a volume ratio of 1:1-1:3, cleaning for 20min, and then washing with pure water. The oil stain and other impurities generated in the high-temperature baking process can be further removed by cleaning the mixed solution of sulfuric acid and hydrogen peroxide.
e) On BCl using inductively coupled plasma etcher (ICP)3With Cl2And etching the epitaxial wafer for 10-30S in the mixed gas environment. The GaN impurities 3 on the sapphire patterned substrate 2 can be further removed by ICP etching. The structure shown in fig. 3 is finally obtained.
f) And ultrasonically treating the etched epitaxial wafer in an acetone solution for 10min, and then washing with pure water.
g) And (4) rinsing the treated epitaxial wafer by using pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min.
Through the cleaning of the acetone solution and the ethanol solution, oil stains and other impurities on the surface of the epitaxial wafer can be further cleaned, so that the surface of the epitaxial wafer is clean.
The method of the invention is that an epitaxial layer is directly grown on a sapphire pattern substrate 2 without growing a layer of high-melting-point material easy to corrode and a first layer of high-melting-point material with stability, so that the epitaxial growth is simplified, a GaN layer 1 is removed by adopting a physical baking method of a high-temperature furnace without any damage to the sapphire substrate, then the surface of the substrate is cleaned by a wet method, and then inductively coupled plasma etching (ICP), BCl are used for etching3With Cl2The residual GaN impurity 3 is removed by etching the mixed gas, the process method is simple, the substrate is not damaged, and the cost is saved.
Because the GaN layer 2 is removed by adopting a physical baking method, the substrate is not damaged, the process is simple, and the substrate is not easy to be polluted. And the substrate is cleaned by a wet method and ICP (inductively coupled plasma) and the residual GaN impurities 3 are removed, so that the requirement of a new substrate is met and the cost is saved.
Example 1:
the temperature of the high temperature furnace in the step a) is 1500 ℃, and the baking time is 3 hours.
Example 2:
the volume ratio of the sulfuric acid to the hydrogen peroxide in the step d) is 1: 2.
Example 3:
the etching time in step e) was 10S.
The invention is further verified below by applying test examples:
the sapphire patterned substrate 2 recovered by the method of the present invention is compared with a brand new sapphire patterned substrate. Through microscope observation, the GaN layer 1 on the surface of the sapphire patterned substrate 2 recovered by the method is completely removed and is consistent with the surface of a new sapphire patterned substrate, so that the sapphire patterned substrate can be repeatedly grown and utilized.

Claims (4)

1. A method for recovering a sapphire patterned substrate for a GaN-LED by combining physics and chemistry is characterized by comprising the following steps:
a) baking the waste epitaxial wafer in a high-temperature furnace at the high temperature of 1000-2000 ℃ for 3-6 hours;
b) taking out the baked epitaxial wafer from the high-temperature furnace, and putting the epitaxial wafer into an acetone solution for ultrasonic treatment for 10 min;
c) rinsing the treated epitaxial wafer with pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min;
d) placing the epitaxial wafer into a mixed solution of sulfuric acid and hydrogen peroxide with a volume ratio of 1:1-1:3, cleaning for 20min, and then washing with pure water;
e) BCl using inductively coupled plasma etcher3With Cl2Etching the epitaxial wafer for 10-30S in the mixed gas environment;
f) carrying out ultrasonic treatment on the etched epitaxial wafer in an acetone solution for 10min, and then washing the epitaxial wafer by using pure water;
g) and (4) rinsing the treated epitaxial wafer by using pure water, and then putting the treated epitaxial wafer into an ethanol solution for ultrasonic treatment for 10 min.
2. The method for recovering a sapphire patterned substrate for GaN-LED in combination of physics and chemistry according to claim 1, wherein: the temperature of the high temperature furnace in the step a) is 1500 ℃, and the baking time is 3 hours.
3. The method for recovering a sapphire patterned substrate for GaN-LED in combination of physics and chemistry according to claim 1, wherein: the volume ratio of the sulfuric acid to the hydrogen peroxide in the step d) is 1: 2.
4. The method for recovering a sapphire patterned substrate for GaN-LED in combination of physics and chemistry according to claim 1, wherein: the etching time in step e) was 10S.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102005518B (en) * 2010-08-25 2012-01-04 山东华光光电子有限公司 Method for preparing pyramidal patterned substrate through twice corrosion
CN102522467A (en) * 2012-01-04 2012-06-27 南京大学扬州光电研究院 Preparation method of submicron-grade graph on sapphire substrate
CN104362083B (en) * 2014-11-17 2017-10-31 山东元旭光电股份有限公司 Graphical sapphire substrate scraps the Sapphire Substrate reuse method of epitaxial wafer

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* Cited by examiner, † Cited by third party
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WO2007050736A2 (en) * 2005-10-26 2007-05-03 Velox Semiconductor Corporation Vertical structure semiconductor devices and method of fabricating the same
US7682937B2 (en) * 2005-11-25 2010-03-23 Advanced Laser Separation International B.V. Method of treating a substrate, method of processing a substrate using a laser beam, and arrangement

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102005518B (en) * 2010-08-25 2012-01-04 山东华光光电子有限公司 Method for preparing pyramidal patterned substrate through twice corrosion
CN102522467A (en) * 2012-01-04 2012-06-27 南京大学扬州光电研究院 Preparation method of submicron-grade graph on sapphire substrate
CN104362083B (en) * 2014-11-17 2017-10-31 山东元旭光电股份有限公司 Graphical sapphire substrate scraps the Sapphire Substrate reuse method of epitaxial wafer

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