CN103834999B - A kind of method of preparing gallium nitride monocrystal substrate by precrack - Google Patents
A kind of method of preparing gallium nitride monocrystal substrate by precrack Download PDFInfo
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Abstract
The invention discloses a kind of method of preparing gallium nitride monocrystal substrate by precrack. The present invention adopts together with the technological incorporation such as a precrack, MOCVD, HVPE and Stress Control self-separation, edge to foreign substrate is processed, then optimize MOCVD growth technique, match with concrete precrack method, introduce gap as precrack in the edge at the interface of GaN/ foreign substrate; Realize the graded of plane stress from edge to center by stress control technique; Under certain gradient stress effect, the complete self-separation of GaN and foreign substrate, thus obtain the complete GaN single crystalline substrate of large scale. The present invention obtains Free-standing GaN single crystalline substrate, smooth surface flawless, and crystal mass is high. The present invention has realized the GaN of original position and the self-separation of foreign substrate, does not need the other equipment and technology such as complicated laser lift-off or plated metal sacrifice layer, and technique is simple, is easy to control, and has greatly improved practicality of the present invention.
Description
Technical field
The present invention relates to photoelectric material and devices field, be specifically related to a kind of method of preparing gallium nitride monocrystal substrate by precrack.
Background technology
Gallium nitride GaN base III/V group-III nitride is the semiconductor material with wide forbidden band of important direct band gap, and semiconductor devices under blue, green, purple, ultraviolet light and the opto-electronic device such as white light emitting diode LED, short wavelength laser diode LD, ultraviolet light detector and power electronic device and electronic device and specific condition etc. has wide practical use in field.
Due to high melting temperature and higher nitrogen saturated vapour pressure, make to prepare large area GaN monocrystalline very difficult, the heteroepitaxial growth GaN base device on the substrate such as sapphire or carborundum of large mismatch of having to. Although this heterogeneous epitaxial technology based on cushion technology has been obtained huge success, but this method can not be given full play to the superior performance of GaN base semiconductor material, its subject matter is: owing to having larger lattice mismatch and thermal stress mismatch between GaN and sapphire, cause thus 10 1.9cm-2Misfit dislocation, have a strong impact on crystal mass, reduce the luminous efficiency of LED; 2. sapphire is insulator, and under normal temperature, resistivity is greater than 1011Ω cm, so just cannot make the device of vertical stratification, conventionally can only make N-type and P type electrode at epitaxial layer upper surface, therefore make efficient lighting area reduce, and has increased photoetching and etching process in device preparation simultaneously, and the utilization rate of material is reduced; 3. sapphire heat conductivility is bad, is about 0.25W/cmK 100 DEG C of thermal conductivities, and this performance impact for GaN base device is very large, and particularly, in large area high power device, heat dissipation problem is very outstanding; 4. in the making of GaN base laser, because sapphire hardness is very high, and between sapphire lattice and GaN lattice, there is the angle of one 30 degree, so be difficult to obtain the cleavage surface of GaN base LD epitaxial layer, the chamber face that also just can not obtain by the method for cleavage GaN base LD, therefore GaN single crystalline substrate also has particular importance meaning for the making of GaN base laser. Based on above reason, further improve and development of new GaN base semiconductor laser, high-power and high-luminance LED, High-Power Microwave device etc. for semiconductor lighting, its only way which must be passed is the GaN monocrystalline homo-substrate material of use fabricating low-defect-density and controllable optical, electrology characteristic.
The method of growing GaN single crystalline substrate comprises the methods such as high temperature and high pressure method, the hot method of ammonia, sodium flux growth metrhod and hydride vapour deposition (Hydridevapor～phaseepitaxy) HVPE at present. First three methods, high temperature and high pressure method, the hot method of ammonia and sodium flux method, or need high-temperature high-pressure apparatus, or need sodium potassium isoreactivity molten mass, dangerous large, research unit is few. All can only obtain 10 millimeters of magnitude crystal in beginning time more than ten years, substantially can not use as substrate, be mainly used for the research of material fundamental property. HVPE growing technology is due to advantages such as its equipment is relatively simple, cost is low, fast growths, and even, large scale GaN/Al can grow2O3Thick film compound substrate. Then, removing the foreign substrate such as sapphire by methods such as laser lift-offs, can obtain Free-standing GaN single crystalline substrate, is the main flow technology of preparing of current GaN single crystalline substrate.
HVPE prepares GaN single crystalline substrate, and the main problem facing is how GaN single-crystal thick films to be separated with foreign substrate such as sapphires. For separating of GaN single-crystal thick films and substrate, mainly contain: the method for laser lift-off (laserlift-off), use LASER HEATING Sapphire Substrate and GaN single-crystal thick films interface, GaN single-crystal thick films is separated; The method of sacrificial substrate (SacrificialSubstrate), main thought is the substrate that can remove by the method for chemical attack or etching by using, as metal, GaAs or Si substrate, obtains Free-standing GaN single crystalline substrate; Self-separation technology (self-separation), main thought is by various cushions, insert layer or nano graph layer, regulate and make stress concentrate on these insert layer places in conjunction with growth conditions, make spontaneous the stripping down from Sapphire Substrate of GaN single-crystal thick films at temperature-fall period. But all there is equipment complexity in these methods, separation difficulty, the shortcoming such as GaN single-crystal thick films is easily broken, and yield rate is low, makes holding at high price of GaN single crystalline substrate.
Summary of the invention
For above problems of the prior art, the present invention proposes a kind of method of preparing more at low cost large area GaN single crystalline substrate by precrack self-separation.
The object of the present invention is to provide a kind of method of preparing gallium nitride monocrystal substrate by precrack.
The preparation method of gallium nitride monocrystal substrate of the present invention, comprises the following steps:
1) in foreign substrate, adopt metal organic-matter chemical gaseous phase deposition MOCVD method growing GaN monocrystal thin films, and match with precrack method, in edge's introducing gap at the interface of GaN monocrystal thin films and foreign substrate as precrack; 2) in the GaN/ foreign substrate with precrack, utilize hydride vapour deposition HVPE method growing GaN single-crystal thick films, in growth course, adopt stress control technique, control GaN single-crystal thick films and grow into certain thickness, make the internal stress in GaN single-crystal thick films reach maximum;
3) in the time making internal stress in GaN single-crystal thick films reach maximum, stop growing, and start to lower the temperature, control thermograde and Temperature Distribution in temperature-fall period, utilize the coefficient of thermal expansion differences between GaN single-crystal thick films and foreign substrate, the stress distribution in GaN single-crystal thick films is reduced from edge to center degree of passing;
4) stress that in GaN single-crystal thick films, degree of passing changes causes the interface of GaN and foreign substrate first to occur shearing force in edge, in precrack constantly inwardly expansion under this shearing force effect of the edge at interface, GaN is separated to center automatically from edge, thereby obtain the Free-standing GaN single crystalline substrate of self-separation.
Wherein, in step 1), precrack method refers to be utilized photoetching, etching, covers and the Chemical Physics method such as corrosion, edge at the interface of foreign substrate and GaN monocrystal thin films introduces gap, form V-type or U-shaped otch, the bottom surface of otch is parallel to interface, can be used as the formation of crack of next step separation. Precrack method comprises horizontal extension method, hangs epitaxy, substrate graph method and additional baffle plate method, can a kind of method uses separately or two or more method is combined use. Horizontal extension method refers to utilizes conventional plasma enhanced chemical vapor deposition method PECVD, photoetching or etching method to form mask at the surrounded surface of foreign substrate, and mask is along the edge of foreign substrate to 20～1000 microns of insied widths, height 20～500 nanometers; Then, adjust MOCVD growth technique, make foreign substrate the GaN of masked areas growth exceed the thickness of mask, the cross growth on mask of its edge, the width of cross growth is less than the width of mask; After MOCVD growth finishes, all remove mask by the method for corrosion, thereby at edge's formation precrack at the interface of GaN monocrystal thin films and foreign substrate. Hang epitaxy and refer to first with 0.5～2 micron of left and right GaN of MOCVD growth, then form mask at centre of surface large area region, only at edge, 20～1000 microns of regions do not have mask; There is no the GaN of mask protection with wet etching or reaction coupled plasma (InductivelyCoupledPlasma) ICP etching edge, etch into the interface of foreign substrate always, adjust etching technics and make etching edge steep; The mask on erosion removal surface, continues MOCVD growing GaN monocrystal thin films, 1～10 micron of thickness, and adjusting process makes sidewall hang growth to be inverted triangle shape, thereby at edge's formation precrack at the interface of GaN monocrystal thin films and foreign substrate. Substrate graph method refers at the fringe region of foreign substrate carries out graphical treatment, the shape of figure can be the various shapes such as circle, triangle, column, polygon, object is to make this part region be difficult for MOCVD epitaxial growth to go out GaN, inside 20～1000 microns along the edge of foreign substrate of the width of patterned area; Then MOCVD growing GaN monocrystal thin films in the foreign substrate of crossing in graphical treatment, 1～10 micron of thickness, the adjusting process cross section that makes to grow is inverted triangle shape, thereby forms precrack in the edge at the interface of GaN monocrystal thin films and foreign substrate. Additional baffle plate method refer to adopt can corrosion-and high-temp-resistant material be made into ring-shaped baffle; Ring-shaped baffle is placed in foreign substrate, covers the surrounded surface of foreign substrate; After epitaxial growth certain thickness GaN monocrystal thin films, remove baffle plate, form precrack in the edge at interface. In these methods, MOCVD growth technique all need to be with concrete condition adjustment.
In step 2) in, stress control technique comprises that gradual change modulation, periodic modulation, low temperature insert layer and hydrogen chloride anti-carve the method that reduces stress in the growth courses such as erosion. The wherein visible patent No.201010527353.9 of details of gradual change modulation and periodic modulation technology. Low temperature insert layer is current techique, i.e. short time growing GaN at low temperatures in growth course, and then be raised to high temperature continued growth; Low temperature insert layer can be inserted also and can multilayer insert by individual layer. The anti-etching method of hydrogen chloride is in growing GaN process, to suspend growth, passes into separately HCl gas etching is carried out in GaN surface, and then continue the method for GaN growth. Wherein certain thickness refers to that the thickness of GaN single-crystal thick films reaches 0.2～1.5 times of thickness of foreign substrate.
In step 3), the scope of temperature degree of passing is 10～200 DEG C/min; The scope of Temperature Distribution is 0.01～50 DEG C/mm.
In step 4), in precrack constantly inwardly expansion under shearing force effect of the edge at the interface of GaN single-crystal thick films and foreign substrate, GaN is separated to center automatically from edge, obtain the large-sized Free-standing GaN single crystalline substrate of self-separation, thickness 0.1～the 1.0mm of the GaN single crystalline substrate separating, remains in the thickness 0.01～0.3mm of the GaN in foreign substrate.
The present invention proposes 2 inches of GaN substrate preparation methods of self-supporting that the methods such as precrack, MOCVD, HVPE and Stress Control self-separation are merged. By precrack method, comprise horizontal extension method, hang epitaxy, substrate graph method, additional baffle plate method etc., edge to foreign substrate such as sapphires is processed, then optimize MOCVD growth technique, match with concrete precrack method, the edge at the final interface in GaN/ foreign substrate introduces gap as precrack (being parallel to interface), is characterized in the time being subject to larger effect of stress easily along the Directional Extension that is parallel to interface. Thermal stress in lattice mismatch stress and the temperature-fall period of this larger stress main source HVPE growing GaN single-crystal thick films. In HVPE thick film growth subsequently and temperature-fall period, realize the graded of plane stress from edge to center by stress control technique. Due to the edge at interface be prepared with precrack, can play delamination crack source, under certain gradient stress effect, easily along Parallel Interfaces expansion, cause the complete self-separation of GaN and foreign substrate, thereby obtain the complete GaN single crystalline substrate of large scale. Advantage of the present invention:
The present invention adopts a kind of preparation method who causes more cheaply the GaN single crystalline substrate of self-separation by precrack method, successfully obtains 2 inches of transparent Free-standing GaN single crystalline substrate of self-separation, smooth surface flawless, and crystal mass is high, and thickness reaches 320 μ m. The present invention has realized the GaN of original position and the self-separation of foreign substrate, does not need the other equipment and technology such as complicated laser lift-off or plated metal sacrifice layer, and technique is simple, is easy to control, and has greatly improved practicality of the present invention.
Brief description of the drawings
Fig. 1 is that the present invention adopts horizontal extension method to form the schematic diagram of the technological process of precrack in the edge at the interface of foreign substrate and GaN monocrystal thin films;
Fig. 2 is that the present invention adopts suspension epitaxy to form the schematic diagram of the technological process of precrack in the edge at the interface of foreign substrate and GaN monocrystal thin films;
Fig. 3 is that the present invention adopts additional baffle plate method to form the schematic diagram of the technological process of precrack in the edge at the interface of foreign substrate and GaN monocrystal thin films;
Fig. 4 is the design sketch that adopts 2 inches of Free-standing GaN single crystalline substrate of precrack method acquisition of the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
Embodiment mono-
The present embodiment adopts the preparation method of the gallium nitride monocrystal substrate of horizontal extension method, comprises the following steps:
1) in foreign substrate, adopt metal organic-matter chemical gaseous phase deposition MOCVD method growing GaN monocrystal thin films, and match with precrack method, in the introducing gap, circular edge place at the interface of the foreign substrate of GaN monocrystal thin films and c surface sapphire as precrack:
A) adopt conventional plasma enhanced chemical vapor deposition method PECVD, photoetching and lithographic technique to form two silicon nitride SiO at the surrounded surface of sapphire foreign substrate 12Mask 21: first, with the surface of acetone, alcohol and the commercial sapphire foreign substrate of washed with de-ionized water, put into PECVD reative cell and deposit SiO cleaning sapphire foreign substrate2Film, thickness 20～500 nanometers; Then, utilize photoetching and erosion removal SiO2Film, surface is except other SiO of fringe region2Film is erosion removal all, in foreign substrate circumferential edges certain width, forms SiO2Mask 21, mask 21 is along the edge of foreign substrate 1 to 20～1000 microns of insied widths, as shown in Fig. 1 (a);
B) put into MOCVD reative cell and carry out a secondary growth, form GaN monocrystal thin films 3: be first warmed up to the cushion lower than the temperature growing low temperature of 600 DEG C, the thickness of cushion is between 10～60 nanometers; And then be raised to high growth temperature GaN between 900～1100 DEG C, when the thickness of GaN exceedes SiO2When the height of mask, by controlling V/III than to improve GaN cross growth speed, make GaN at SiO2Mask surface cross growth, the SiO of covering fringe region2Mask, forms GaN monocrystal thin films 3, as shown in Fig. 1 (b);
C) after erosion removal SiO2 mask formation precrack: MOCVD growth finishes, put into HF acid, remove whole SiO2 masks by the method for HF acid corrosion, thereby form precrack 2 in the edge at the interface of GaN and sapphire foreign substrate, as shown in Fig. 1 (c);
2) carry out carrying out surface treatment before HVPE growth, comprise the removal of organic washing and oxide layer; Then, put into hvpe reactor chamber and carry out diauxic growth, form GaN single-crystal thick films 4: control the continued growth of GaN monocrystal thin films, in growth course, need the stress control technique that adopts gradual change modulation to add periodic modulation method to prevent the generation of crackle in GaN single-crystal thick films, ensure high crystal mass and surface quality simultaneously, stress can increase gradually with the increase of thickness, and the thickness of controlling the GaN single-crystal thick films 4 of HVPE growth reaches 0.2～1.5 times of Sapphire Substrate thickness, as shown in Figure 1 (d) shows;
3) in the time that GaN single-crystal thick films grows into the thickness of stress maximum, start temperature-fall period: strictly control thermograde and Temperature Distribution in temperature-fall period, make the temperature degree of passing of cooling control to 10～200 DEG C/min, radial temperature profile controls to 0.01～50 DEG C/mm, utilize the coefficient of thermal expansion differences between GaN single-crystal thick films and foreign substrate, the stress distribution in GaN single-crystal thick films is reduced from edge to center degree of passing;
4) first there is shearing force by the interface that causes GaN and foreign substrate in edge in the stress that the degree of passing in GaN single-crystal thick films changes, the crackle prefabricated at interface edge place is in constantly inwardly expansion of this shearing force effect, GaN is separated to center automatically from edge, obtain 2 inches of Free-standing GaN single crystalline substrate of self-separation.
Adopt the present embodiment, obtained 2 inches of complete flawless GaN single crystalline substrate of self-separation, as shown in Figure 4.
Embodiment bis-
The present embodiment adopts the preparation method of the gallium nitride monocrystal substrate that hangs epitaxy, comprises the following steps:
1) a) with the surface of acetone, alcohol and the commercial sapphire foreign substrate of washed with de-ionized water; Put into MOCVD equipment reaction chamber by cleaning sapphire substrate, at sapphire foreign substrate surface epitaxial growth of gallium nitride 31,0.5～2 micron of thickness, as Fig. 2 (a);
B) put into subsequently PECVD reative cell and deposit SiO2Film, thickness 20～500 nanometers of film; Then, utilize photoetching and HF acid, by the SiO in 20～1000 microns of regions of foreign substrate circumferential edges2Thin film corrosive is removed, and retains SiO at centre of surface large area region2, form mask 22, as shown in Fig. 2 (b);
C) adopt ICP etching edge there is no SiO2The GaN of protection etches into GaN and sapphire interface always, adjusts etching technics and makes etching edge steep, and etching circle ring area width is 20～1000 microns, as shown in Figure 2 (c);
D) adopt HF acid corrosion to remove SiO2Mask, as shown in Figure 2 (d) shows;
E) putting into MOCVD reative cell grows for the second time, 1～10 micron of thickness, form GaN monocrystal thin films 3, adjusting process makes sidewall suspension growth be inverted triangle shape, thereby between GaN monocrystal thin films 3 and sapphire foreign substrate 1, interface boundary place forms precrack 2, as shown in Fig. 2 (e);
2) before HVPE growth, carry out surface treatment, comprise organic washing and oxide layer removal; Then, put into hvpe reactor chamber and carry out HVPE growth, form GaN single-crystal thick films: control the continued growth of GaN monocrystal thin films, in growth course, need the stress control technique that adopts gradual change modulation to add the method for periodic modulation to prevent the generation of crackle in GaN single-crystal thick films, ensure high crystal mass and surface quality simultaneously, stress can increase gradually with the increase of thickness, the thickness of controlling the GaN single-crystal thick films of HVPE growth reaches 0.2～1.5 times of sapphire foreign substrate thickness, as shown in Fig. 2 (f);
3) in the time that GaN single-crystal thick films grows into the thickness of stress maximum, start temperature-fall period: strictly control thermograde and Temperature Distribution in temperature-fall period, make the temperature degree of passing of cooling control to 10～200 DEG C/min, radial temperature profile controls to 0.01～50 DEG C/mm, utilize the coefficient of thermal expansion differences between GaN single-crystal thick films and foreign substrate, the stress distribution in GaN single-crystal thick films is reduced from edge to center degree of passing;
4) first there is shearing force by the interface that causes GaN and foreign substrate in edge in the stress that the degree of passing in GaN single-crystal thick films changes, the crackle prefabricated at interface edge place is in constantly inwardly expansion of this shearing force effect, GaN is separated to center automatically from edge, obtain 2 inches of Free-standing GaN single crystalline substrate of self-separation.
Embodiment tri-
The present embodiment adopts the preparation method of the gallium nitride monocrystal substrate of additional baffle plate method, comprises the following steps:
1) a) with the surface of acetone, alcohol and the commercial sapphire foreign substrate of washed with de-ionized water, put into MOCVD reative cell by cleaning sapphire foreign substrate, annular baffle 23 is placed on sapphire, sapphire fringe region is covered, capped circle ring area width is 20～1000 microns, as shown in Fig. 3 (a);
B) then at sapphire surperficial epitaxial growth GaN monocrystal thin films 3,0.5～4 micron of thickness, as shown in Figure 3 (b); Circular baffle plate, the material of the energy corrosion-and high-temp-resistants such as available metal molybdenum, quartz or graphite is made, and is made up of two semicircular ring, to remove;
C) take out sample, two Semicircular baffles are carefully taken out, thereby at edge's formation precrack 2 at the interface of GaN monocrystal thin films and sapphire foreign substrate, as shown in Figure 3 (c);
2) before HVPE growth, carry out surface treatment, comprise organic washing and oxide layer removal; Then, put into hvpe reactor chamber and carry out HVPE growth, form GaN single-crystal thick films: control the continued growth of GaN monocrystal thin films, in growth course, need the stress control technique that adopts gradual change modulation to add the method for periodic modulation to prevent the generation of crackle in GaN single-crystal thick films, ensure high crystal mass and surface quality simultaneously, stress can increase gradually with the increase of thickness, the thickness of controlling the GaN single-crystal thick films of HVPE growth reaches 0.2～1.5 times of sapphire foreign substrate thickness, as shown in Fig. 2 (f);
3) in the time that GaN single-crystal thick films grows into the thickness of stress maximum, start temperature-fall period: strictly control thermograde and Temperature Distribution in temperature-fall period, make the temperature degree of passing of cooling control to 10～200 DEG C/min, radial temperature profile controls to 0.01～50 DEG C/mm, utilize the coefficient of thermal expansion differences between GaN single-crystal thick films and foreign substrate, the stress distribution in GaN single-crystal thick films is reduced from edge to center degree of passing;
4) first there is shearing force by the interface that causes GaN and foreign substrate in edge in the stress that the degree of passing in GaN single-crystal thick films changes, the crackle prefabricated at interface edge place is in constantly inwardly expansion of this shearing force effect, GaN is separated to center automatically from edge, obtain 2 inches of Free-standing GaN single crystalline substrate of self-separation.
2 inches of Free-standing GaN single crystalline substrate that obtain by above-mentioned preparation method, as shown in Figure 4.
Finally it should be noted that, the object of publicizing and implementing mode is to help further to understand the present invention, but it will be appreciated by those skilled in the art that: without departing from the spirit and scope of the invention and the appended claims, various substitutions and modifications are all possible. Therefore, the present invention should not be limited to the disclosed content of embodiment, and the scope that the scope of protection of present invention defines with claims is as the criterion.
Claims (10)
1. a preparation method for gallium nitride monocrystal substrate, is characterized in that, described preparation method comprises the following steps:
1) in foreign substrate, adopt metal organic-matter chemical gaseous phase deposition MOCVD method growing GaN monocrystal thin films, and withPrecrack method matches, and introduces gap as precrack in the edge at the interface of GaN monocrystal thin films and foreign substrate;
2), in the GaN/ foreign substrate with precrack, utilize hydride vapour deposition HVPE method growing GaN monocrystalline thickFilm, in growth course, adopts stress control technique, controls GaN single-crystal thick films and grows into certain thickness, makes GaNIt is maximum that internal stress in single-crystal thick films reaches;
3) in the time making internal stress in GaN single-crystal thick films reach maximum, stop growing, and start cooling, control in temperature-fall periodThermograde and Temperature Distribution, utilize the coefficient of thermal expansion differences between GaN single-crystal thick films and foreign substrate, makes at GaNStress distribution in single-crystal thick films reduces from edge to center gradient;
4) in GaN single-crystal thick films, the stress of graded causes the interface of GaN and foreign substrate first to occur shearing force in edge,In precrack constantly inwardly expansion under this shearing force effect of the edge at interface, make GaN automatic to center from edgeSeparate, thus the Free-standing GaN single crystalline substrate of acquisition self-separation.
2. preparation method as claimed in claim 1, is characterized in that, in step 1) in, precrack method refer to utilize photoetching,Etching, the Chemical Physics method of covering and corroding, introduce gap in the edge at the interface of foreign substrate and GaN monocrystal thin films,Form V-type or U-shaped otch, the bottom surface of otch is parallel to interface; Precrack method comprise horizontal extension method, hang epitaxy,Substrate graph method and additional baffle plate method, above each method uses separately or two or more method is combined use.
3. preparation method as claimed in claim 2, is characterized in that, described horizontal extension method refers to utilizes conventional plasma to increaseExtensive chemical vapour deposition process PECVD, photoetching or etching method form mask at the surrounded surface of foreign substrate, and mask is along foreign substrateEdge to 20～1000 microns of insied widths, height 20～500 nanometers; Then, adjust MOCVD growth technique, make heterogeneousThe substrate GaN that masked areas is not grown exceedes the thickness of mask, the cross growth on mask of its edge, and the width of cross growth is littleIn the width of mask; After MOCVD growth finishes, all remove mask by the method for corrosion, thus at GaN monocrystal thin films andThe edge at the interface of foreign substrate forms precrack.
4. preparation method as claimed in claim 2, is characterized in that, described suspension epitaxy refers to first with MOCVD growth 0.5～2Micron GaN, then forms mask in centre of surface region, at edge, 20～1000 microns of regions do not have mask; Use wet etchingOr reaction coupled plasma ICP etching edge do not have the GaN of mask protection, etch into the interface of foreign substrate always, adjustWhole etching technics makes etching edge steep; The mask on erosion removal surface, continues MOCVD growing GaN monocrystal thin films, thickness1～10 micron, adjusting process makes sidewall hang growth to be inverted triangle shape, thereby at the interface of GaN monocrystal thin films and foreign substrateEdge form precrack.
5. preparation method as claimed in claim 2, is characterized in that, described substrate graph method refers to the marginal zone in foreign substrateGraphical treatment is carried out in territory, and the shape of figure comprises circle, triangle, column, polygon, makes this part region be difficult for MOCVDEpitaxial growth goes out GaN, inside 20～1000 microns along the edge of foreign substrate of the width of patterned area; Then at graphical placeMOCVD growing GaN monocrystal thin films in the foreign substrate of managing, 1～10 micron of thickness, the adjusting process cross section that makes to grow is downTriangular shape, thus precrack formed in the edge at the interface of GaN monocrystal thin films and foreign substrate.
6. preparation method as claimed in claim 2, is characterized in that, described additional baffle plate method refers to adopting corrosion-and high-temp-resistantMaterial is made into ring-shaped baffle; Ring-shaped baffle is placed in foreign substrate, covers the surrounded surface of foreign substrate; Epitaxial growthAfter GaN monocrystal thin films, remove baffle plate, form precrack in the edge at interface.
7. preparation method as claimed in claim 1, is characterized in that, in step 2) in, stress control technique comprise gradual change modulation,Periodic modulation, low temperature insert layer and hydrogen chloride anti-carve the method that reduces stress in the growth course of erosion.
8. preparation method as claimed in claim 1, is characterized in that, in step 2) in, wherein said certain thickness refers to GaNThe thickness of single-crystal thick films reaches 0.2～1.5 times of thickness of foreign substrate.
9. preparation method as claimed in claim 1, is characterized in that, in step 3) in, the scope of thermograde is 10～200 DEG C/min;The scope of Temperature Distribution is 0.01～50 DEG C/mm.
10. preparation method as claimed in claim 1, is characterized in that, in step 4) in, the GaN single crystalline substrate separatingThickness 0.1～1.0mm, remain in the thickness 0.01～0.3mm of the GaN in foreign substrate.
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| CN112164976A (en) * | 2020-09-29 | 2021-01-01 | 北京大学东莞光电研究院 | High-heat-dissipation GaN single crystal substrate and preparation method thereof |
| CN113984469A (en) * | 2021-10-26 | 2022-01-28 | 长江存储科技有限责任公司 | Sample and method for preparing same |
| CN114892264B (en) * | 2022-05-17 | 2024-03-05 | 镓特半导体科技(铜陵)有限公司 | Gallium nitride substrate, gallium nitride single crystal layer, and method for producing same |
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