CN113445131A - Method for inhibiting defects from gallium nitride seed crystal, gallium nitride single crystal and application - Google Patents

Method for inhibiting defects from gallium nitride seed crystal, gallium nitride single crystal and application Download PDF

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CN113445131A
CN113445131A CN202110719050.5A CN202110719050A CN113445131A CN 113445131 A CN113445131 A CN 113445131A CN 202110719050 A CN202110719050 A CN 202110719050A CN 113445131 A CN113445131 A CN 113445131A
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gallium nitride
seed crystal
seed
dislocation
crystal
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赵呈春
杭寅
龚巧瑞
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Shanghai Institute of Optics and Fine Mechanics of CAS
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Abstract

The invention provides a method for inhibiting defects from gallium nitride seed crystals, a gallium nitride single crystal and application. The method comprises the following steps: firstly, polishing the surface of the used gallium nitride seed crystal, and corroding the seed crystal by adopting corrosive liquid to generate dislocation corrosion pits at dislocation positions on the surface of the seed crystal. And then depositing a layer of covering material on the surface of the seed crystal. And then removing the covering material on the outer surface of the etch pit in the step by adopting a mechanical polishing method, and finally performing crystal growth by using the seed crystal to obtain the gallium nitride single crystal. The method for inhibiting the defects from the gallium nitride seed crystal, the gallium nitride single crystal and the application can realize effective inhibition on dislocation defects, simultaneously achieve full utilization of dislocation-free areas, and have the advantages of simple steps and lower cost.

Description

Method for inhibiting defects from gallium nitride seed crystal, gallium nitride single crystal and application
Technical Field
The invention belongs to the field of preparation of crystal materials. And more particularly to a method for suppressing defects from a gallium nitride seed crystal, a gallium nitride single crystal and applications.
Background
Gallium nitride (GaN) is a wide band gap semiconductor material, has a forbidden band width of 3.4eV, has the characteristics of high saturated electron drift velocity and high breakdown voltage, is an ideal material for manufacturing blue and green light emitting diodes and laser diodes, and has a great potential in the market demand of power devices and electronic and electric power devices. Research on GaN devices grown by heteroepitaxy has achieved a great result, and some devices have been commercialized, but GaN grown by heteroepitaxy has a high defect density, which limits its application in high-power and high-frequency devices. The homoepitaxy is carried out by adopting a high-quality GaN single crystal material as the substrate, so that the dislocation density in the epitaxial layer can be effectively reduced, and the influence of defects on the device can be effectively reduced. Currently, commonly used GaN crystal growth methods include a Hydride Vapor Phase Epitaxy (HVPE) method, an ammonothermal method, a co-solvent method, or a high-pressure solution method. The HVPE method has fast growth rate, easy obtaining of large-size crystal, high cost and high dislocation density (more than 10)5cm-2) And small curvature radius. The ammonothermal method has high crystallization quality and low dislocation density, can grow on a plurality of seed crystals simultaneously, can perform large-scale production to reduce cost, but has higher growth pressure and low growth rate. The flux method has mild growth conditions and low requirements on growth equipment, but polycrystal is easily formed in the growth process. The high pressure solution process requires high growth temperatures (above 1500 ℃) and extremely high pressures (greater than 1GPa), resulting in high growth equipment requirements and high costs.
One of the major contributors to the dislocation density of GaN crystals grown by either growth method is the GaN seed crystal used, and dislocations in the GaN single crystal seed crystal will extend from the growth direction into the newly grown GaN crystal. Methods have been developed to reduce the effects of defects from the seed, such as by covering a portion of the seed surface with a material having a periodic pore structure. The GaN crystal growing in the uncovered region does not grow, and the GaN crystal growing in the uncovered region grows laterally and is combined to form a GaN single crystal. Since dislocation defects of the covered portion of the seed crystal are blocked and do not extend into the newly grown GaN crystal, and lateral growth does not generate new dislocations, the technique can reduce the dislocation density of the newly grown crystal to some extent. However, this method has the following disadvantages: (1) the preparation of the periodic hole structure usually needs to adopt semiconductor processes such as photoetching and the like, so that the cost is high and the efficiency is low; (2) the porous structure covers the surface of the seed crystal indiscriminately, and the covered part has a large number of dislocation-free surfaces which cannot participate in the growth of new crystals, thereby causing the waste of the seed crystal; (3) the uncovered areas still have a large number of dislocation defects that still extend into the newly grown crystal. Aiming at the problems, the invention utilizes the basic principle that the covering material blocks dislocation extension according to the special appearance of the dislocation corrosion pit of the GaN crystal and combines with precision processing, can effectively inhibit the dislocation defect without influencing the utilization of the high-quality surface of the seed crystal except the dislocation defect, and can greatly improve the inhibition efficiency of the dislocation defect of the seed crystal.
Disclosure of Invention
The invention provides a novel method for inhibiting defects from gallium nitride seed crystals, which mainly solves the problems of high cost, waste of defect-free areas of the seed crystals, insufficient inhibition of dislocation defects and the like of a common porous pattern covering method.
The invention provides a method for inhibiting defects from gallium nitride seed crystals, which is characterized in that after the gallium nitride seed crystals are polished and corroded, dislocation corrosion pits are generated at dislocation positions on the surfaces of the seed crystals; depositing a layer of covering material on the upper surface of the seed crystal to enable the covering material to cover the corrosion pit; and removing all covering materials outside the etch pits.
The invention also provides a method for growing the gallium nitride single crystal, which comprises the following steps:
s1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal.
S2, depositing a layer of covering material with the thickness not less than 0.01 micrometer on the surface of the seed crystal by adopting an electron beam evaporation method, a magnetron sputtering method or a vacuum thermal evaporation method.
S3, removing all the covering materials deposited on the surface of the seed crystal except the etch pits in the step S2 by adopting a mechanical polishing method.
S4, growing the crystal by using the seed crystal obtained in the step S3 by adopting an HVPE method, an ammonothermal method, a cosolvent method or a high-pressure solution method to obtain the gallium nitride single crystal.
Devices made from gallium nitride single crystals prepared by the above-described method are also within the scope of the present invention.
Also, it should be understood that various combinations, substitutions and alterations can be made by those skilled in the art without departing from the spirit, spirit and scope of the invention.
The key step of the present invention is the removal of the seed surface capping material except for the dislocation etch pits. The overburden material within the dislocation pits is retained during the polishing process because the pits have a depth. The thickness of the covering material must be moderate, if the thickness of the polishing removal is too thin, the surface of the seed crystal still can be completely covered by the material, so that the subsequent single crystal growth can not be carried out, and if the thickness of the polishing removal is too large, all the covering material in the dislocation corrosion pit and outside the pit is completely removed, so that the effect on dislocation defects is lost. Etch pit depth is related to the type of dislocation, the etch process.
The invention has the beneficial effects that:
1) the technology of combining the deposition of the covering material and the precise polishing is adopted, so that the dislocation defect is accurately inhibited, and meanwhile, the dislocation-free area is fully utilized.
2) Secondly, the invention does not use a complex semiconductor patterning process, has simple steps and lower cost.
3) Compared with a gallium nitride single crystal grown by adopting untreated seed crystals, the dislocation density of the GaN crystal grown by the seed crystals treated by the method disclosed by the invention is lower, and the dislocation density can be reduced by 20-70%.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention for suppressing defects from gallium nitride seed crystals, in which the deposited capping material is thicker and has filled dislocation etch pits.
FIG. 2 is a schematic flow chart of the method for suppressing defects from GaN seed crystals according to the present invention, in which the deposited capping material is thin and does not fill the dislocation etch pits.
The meaning of the reference symbols in the figures: (1) polishing and etching dislocation pits, (2) depositing a covering material, (3) polishing and removing part of the covering material, (4) growing a gallium nitride single crystal by an ammonothermal method, a-dislocations in the seed crystal, b-dislocation etching pits, c-the covering material, d-the covering material left in the dislocation etching pits, and e-newly growing the GaN single crystal.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the present invention are commercially available.
The method for inhibiting the defects from the gallium nitride seed crystal roughly comprises the following steps: firstly, polishing the surface of the used gallium nitride seed crystal, and corroding the seed crystal by adopting corrosive liquid to generate dislocation corrosion pits at dislocation positions on the surface of the seed crystal. And then depositing a layer of covering material on the surface of the seed crystal. Then, the covering material deposited in the step is partially removed by adopting a mechanical polishing method, and finally, the seed crystal is used for carrying out ammonothermal growth to obtain the gallium nitride single crystal.
The flow chart of the invention for inhibiting the defects from the gallium nitride seed crystal is shown in the attached figure 1 or figure 2.
Specific process operations reference is made to the following examples.
Example 1
The flow chart in this embodiment is shown in FIG. 1.
S1, after optical-level polishing is carried out on the surface of the used gallium nitride seed crystal, the seed crystal is corroded by corrosive liquid, so that the surface position of the seed crystal is staggeredDislocation etch pits are generated. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 400 ℃, and the corrosion time is 20 minutes.
S2, depositing a layer of silver with the thickness of 2 microns on the surface of the seed crystal by adopting an electron beam evaporation method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, adopting the seed crystal obtained in the step S3 to carry out ammonothermal growth to obtain the gallium nitride single crystal.
The dislocation density was reduced by 70% relative to untreated gallium nitride seed grown crystals.
Example 2
The flow chart in this embodiment is shown in FIG. 2.
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The mol ratio is 1:1, the temperature is 500 ℃, and the corrosion time is 120 minutes.
S2, depositing a layer of gold with the thickness of 0.01 micrometer on the surface of the seed crystal by adopting a magnetron sputtering method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, adopting the seed crystal obtained in the step S3 to carry out HVPE growth to obtain the gallium nitride single crystal.
The dislocation density was reduced by 40% relative to untreated gallium nitride seed grown crystals.
Example 3
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 600 ℃, and the corrosion time is 90 minutes.
S2, depositing a layer of platinum with the thickness of 1 micron on the surface of the seed crystal by adopting a vacuum thermal evaporation method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, growing the gallium nitride single crystal by adopting the seed crystal obtained in the step S3 through a cosolvent method.
The dislocation density was reduced by 30% relative to untreated gallium nitride seed grown crystals.
Example 4
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 550 ℃, and the corrosion time is 120 minutes.
S2, depositing a layer of iridium with the thickness of 0.06 micrometer on the surface of the seed crystal by adopting a magnetron sputtering method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, adopting the seed crystal obtained in the step S3 to carry out ammonothermal growth to obtain the gallium nitride single crystal.
The dislocation density was reduced by 50% relative to untreated gallium nitride seed grown crystals.
Example 5
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 550 ℃, and the corrosion time is 100 minutes.
S2, depositing a layer of silver with the thickness of 5 microns on the surface of the seed crystal by adopting an electron beam evaporation method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, growing the gallium nitride single crystal by adopting the seed crystal obtained in the step S3 through a high-pressure solution method.
The dislocation density was reduced by 30% relative to untreated gallium nitride seed grown crystals.
Example 6
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The mol ratio is 1:1, the temperature is 400 ℃, and the corrosion time is 120 minutes.
S2, depositing a layer of palladium with the thickness of 0.03 micrometer on the surface of the seed crystal by adopting an electron beam evaporation method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, growing the gallium nitride single crystal by adopting the seed crystal obtained in the step S3 through a cosolvent method.
The dislocation density was reduced by 50% relative to untreated gallium nitride seed grown crystals.
Example 7
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 400 ℃, and the corrosion time is 90 minutes.
S2, depositing a layer of gold-silver alloy with the thickness of 0.08 micrometer on the surface of the seed crystal by adopting a magnetron sputtering method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, adopting the seed crystal obtained in the step S3 to carry out ammonothermal growth to obtain the gallium nitride single crystal.
The dislocation density was reduced by 40% relative to untreated gallium nitride seed grown crystals.
Example 8
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio of the components is 1:1,the temperature was 550 ℃ and the etching time was 80 minutes.
S2, depositing a layer of platinum-palladium alloy with the thickness of 1.5 microns on the surface of the seed crystal by adopting a magnetron sputtering method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, growing the gallium nitride single crystal by adopting the seed crystal obtained in the step S3 through a high-pressure solution method.
The dislocation density was reduced by 55% relative to untreated gallium nitride seed grown crystals.
Example 9
S1, after the surface of the used gallium nitride seed crystal is subjected to optical-level polishing, the seed crystal is corroded by a corrosion liquid, so that dislocation corrosion pits are generated at dislocation positions on the surface of the seed crystal. KOH/Na in molten state at the corrosion level used2O2The molar ratio is 1:1, the temperature is 480 ℃, and the corrosion time is 100 minutes.
S2, depositing a layer of silver-iridium alloy with the thickness of 1.6 microns on the surface of the seed crystal by adopting a vacuum thermal evaporation method.
And S3, removing all covering materials on the surface of the seed crystal except the dislocation etching pits deposited in the step S2 by adopting a mechanical polishing method.
S4, adopting the seed crystal obtained in the step S3 to carry out ammonothermal growth to obtain the gallium nitride single crystal.
S5, adopting the gallium nitride single crystal obtained in the step S4 to carry out gallium nitride homoepitaxy, and preparing the semiconductor laser.

Claims (9)

1. A method for inhibiting defects from gallium nitride seed crystals is characterized in that after polishing and etching treatment is carried out on the gallium nitride seed crystals, dislocation etching pits are generated at dislocation positions on the surfaces of the seed crystals; depositing a layer of covering material on the upper surface of the seed crystal to enable the covering material to cover the corrosion pit; and removing all covering materials outside the etch pits.
2. The method for inhibiting defects from a gallium nitride seed crystal according to claim 1, wherein the polishing and etching of the gallium nitride seed crystal is performed by etching the seed crystal with an etching solution after optical-grade polishing of the surface of the gallium nitride seed crystal.
3. A method for suppressing seed crystal defects from gallium nitride as defined in claim 2, wherein said etching liquid level is molten KOH/Na2O2The molar ratio is 1:1, the temperature is 400-600 ℃, and the corrosion time is 20-120 minutes.
4. A method for suppressing defects from a gallium nitride seed according to claim 1, wherein depositing a layer of a capping material on the upper surface of the seed comprises electron beam evaporation, magnetron sputtering or vacuum thermal evaporation.
5. The method of suppressing seed defects from gallium nitride according to claim 1, wherein the capping material is a film of silver, platinum, iridium, palladium, or gold, or alloys thereof.
6. A method for suppressing seed crystal defects from gallium nitride as recited in claim 1 or claim 4, wherein said cap material has a thickness of not less than 0.01 μm.
7. A gallium nitride single crystal grown using the method of suppressing defects from a gallium nitride seed crystal of any of claims 1-6.
8. The grown gallium nitride single crystal according to claim 7, comprising a Hydride Vapor Phase Epitaxy (HVPE) method, an ammonothermal method, a flux method, or a high pressure solution method.
9. Use of a gallium nitride single crystal according to claim 7 or 8 in a substrate.
CN202110719050.5A 2021-06-28 2021-06-28 Method for inhibiting defects from gallium nitride seed crystal, gallium nitride single crystal and application Withdrawn CN113445131A (en)

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