CN102034693A - Method for preparing stress-free GaN thick film on sapphire patterned substrate - Google Patents

Method for preparing stress-free GaN thick film on sapphire patterned substrate Download PDF

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Publication number
CN102034693A
CN102034693A CN2009102353350A CN200910235335A CN102034693A CN 102034693 A CN102034693 A CN 102034693A CN 2009102353350 A CN2009102353350 A CN 2009102353350A CN 200910235335 A CN200910235335 A CN 200910235335A CN 102034693 A CN102034693 A CN 102034693A
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substrate
thick film
gan thick
sapphire
silicon nitride
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CN2009102353350A
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胡强
段瑞飞
魏同波
杨建坤
霍自强
曾一平
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Institute of Semiconductors of CAS
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Institute of Semiconductors of CAS
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Abstract

The invention relates to a method for preparing a stress-free GaN thick film on a sapphire patterned substrate, which comprises the following steps: 1, depositing a silicon oxide or silicon nitride film on a C-plane sapphire substrate; 2, photoetching bar-shaped silicon oxide or silicon nitride mask patterns in a [11-20] direction on the C-plane sapphire substrate of the deposited silicon oxide or silicon nitride film by the conventional photoetching technology; 3, transferring the photoetched bar-shaped silicon oxide or silicon nitride mask patterns onto the substrate by wet-process etching; 4, removing the silicon oxide or silicon nitride film by corrosion, and cleaning the substrate to obtain a clean sapphire patterned substrate; and 5, directly using a hydride gas-phase epitaxy system to epitaxially grow a GaN thick film on the obtained sapphire patterned substrate, and thus finishing the preparation.

Description

The method of the unstressed GaN thick film of preparation on the sapphire graphical substrate
Technical field
The present invention relates to a kind of method that on the sapphire graphical substrate, prepares unstressed GaN thick film.
Background technology
GaN is to be after the semi-conducting material of representative and the second generation are the semi-conducting material of representative with the GaAs with silicon continue the first generation, the third generation semi-conducting material that develops rapidly.GaN has direct band structure, and energy gap is 3.4eV, also has characteristics such as thermal conductivity height, the electronics saturation drift velocity is big, disruptive field intensity is high, dielectric constant is little.Therefore all have wide practical use in indigo plant, green glow and a plurality of fields such as ultraviolet light-emitting diodes (LED), short wavelength laser diode (LD), ultraviolet detector and power electronic device.
Because the preparation of GaN body monocrystalline is difficulty relatively, is difficult to obtain large scale and mass ratio body monocrystalline GaN substrate preferably, so the epitaxial growth of GaN is normally carried out in the mode of heteroepitaxy.There are very big lattice constant mismatch and thermal expansion coefficient difference between various foreign substrate and nitride, therefore utilize in the nitride epitaxial layer of metal-organic chemical vapor deposition equipment (MOVPE), hydride gas-phase epitaxy (HVPE) or molecular beam epitaxy (MBE) homepitaxy technology growth and have very big stress and a lot of crystal defects, the crystal mass of material is subjected to very big influence, thus deterioration the performance of device.And adopt the patterned substrate technology can alleviate in substrate and the nitride epitaxial layer heteroepitaxial growth because the stress that lattice mismatch causes is avoided the generation of crackle.Graph substrate commonly used at present adopts the technology of dry etching usually, technology cost height, and the material surface damage is big, introduces the contaminating impurity substrate easily.And traditional graph substrate technology can not discharge stress fully, and when the thick film more than the growth 100 μ m, its remaining stress still makes the sample cracking.Directly epitaxial growth district and laterally overgrown district Grown GaN influence each other simultaneously, are unfavorable for the growth of GaN thick film.
Summary of the invention
At problems of the prior art, the object of the present invention is to provide the method for the unstressed GaN thick film of preparation on a kind of novel graph substrate.By only growing the method for growing GaN on the limit, prepared unstressed, the flawless GaN thick film of thickness above 100 μ m at V-shaped groove.Overcome the heteroepitaxy GaN thick film problem of cracking easily, also avoided the problem of contamination of substrate and damage simultaneously.
The invention provides a kind of method that on the sapphire graphical substrate, prepares unstressed GaN thick film, may further comprise the steps:
Step 1: deposit layer of silicon dioxide or silicon nitride film on the C surface sapphire substrate;
Step 2: utilize conventional photoetching technique on the C of deposit silicon dioxide or silicon nitride film surface sapphire substrate, to make bar shaped silicon dioxide or silicon nitride mask graph by lithography along [11-20] direction;
Step 3:, the bar shaped silicon dioxide or the silicon nitride mask graph of photoetching are transferred on the substrate by wet etching;
Step 4: silicon dioxide or silicon nitride film are removed in corrosion, clean substrate, the sapphire graphical substrate that obtains cleaning;
Step 5: directly adopt hydride gas-phase epitaxy system epitaxial growth GaN thick film on resulting sapphire graphical substrate, finish preparation.
Wherein the surface of this sapphire graphical substrate is platform and V-shaped groove shape striped, and it is periodically adjacent, the cross section of this V-shaped groove is isosceles triangle not, this V-shaped groove is a window area, two inclined-planes of V-shaped groove are { the different crystal faces of 1-10k} family of crystal planes, wherein the minor face correspondence is＜1-102〉crystal face, and long limit correspondence is＜1-104〉crystal face.
Wherein the thickness of silicon dioxide or silicon nitride film is 10nm to 5 μ m.
Wherein the width of fringe of bar shaped silicon dioxide or silicon nitride mask graph is 1 to 50 μ m, and the window area width is 1 to 50 μ m.
Wherein wet etching is that sample after adopting sulfuric acid and phosphoric acid mixed liquor to photoetching carries out etching, and etching temperature is 100-400 ℃.
Wherein substrate can also be from spinelle, GaN, AlN, GaAs, Si, SiC, LiAlO 2, LiGaO 2, ZrB 2Or HfB 2Select in the family that forms.
Wherein the width of V-shaped groove is 1 to 50 μ m, and the degree of depth is 0.5 to 20 μ m, is the platform of 0.5 to 50 μ m between two V-shaped grooves.
Wherein there is not platform between two V-shaped grooves.
Wherein the temperature of growing GaN thick film is 600 to 1400 ℃.
Wherein except selecting hydride gas-phase epitaxy method epitaxial growth GaN thick film for use, can also select liquid phase epitaxy for use, metal organic vapor, the method epitaxial growth that the enclosure space gas phase transmits.
Description of drawings
For further specifying concrete technology contents of the present invention, below in conjunction with embodiment and accompanying drawing describes in detail as after, wherein:
Fig. 1 is the schematic diagram schematic cross-section that device prepares on the sapphire graphical substrate in the first embodiment of the invention;
Fig. 2 is the schematic diagram schematic cross-section that device prepares on the sapphire graphical substrate in the second embodiment of the invention.
Embodiment
Embodiment 1
See also shown in Figure 1, the present invention a kind of on the sapphire graphical substrate preparation unstressed GaN thick film method, comprise following steps:
Step 1, on the C surface sapphire substrate deposit layer of silicon dioxide or silicon nitride film (figure does not show); The thickness of wherein said silicon dioxide or silicon nitride film is 10nm to 5 μ m; Chemical vapor deposition techniques evaporation thickness on the C surface sapphire substrate that this example adopts plasma to strengthen is the silicon dioxide film of 300nm.
Step 2, utilize conventional photoetching technique on the C of deposit silicon dioxide or silicon nitride surface sapphire substrate, to make bar shaped silicon dioxide or silicon nitride mask graph by lithography along [11-20] direction; Wherein bar shaped silicon dioxide or silicon nitride mask graph are the direction along [11-20], and this bar shaped silicon dioxide or silicon nitride mask graph are striated, and its width is 1 to 50 μ m; This example adopts the photoetching process of standard to make the bar shaped earth silicon mask figure of edge [11-20] direction by lithography on Sapphire Substrate, standard technologies such as this photoetching process comprises gluing, exposure, etching silicon dioxide, remove photoresist, what etching silicon dioxide adopted is the method for reactive ion etching; The width of the earth silicon mask layer striped for preparing is 4 μ m, and the window area width is 3 μ m.
Step 3, by wet etching, the bar pattern of photoetching is transferred on the C surface sapphire substrate; Sample after wherein wet etching adopts sulfuric acid and phosphoric acid mixed liquor to photoetching corrodes, and corrosion temperature is 100-400 ℃; It is the corrosive liquid that 3: 1 the concentrated sulfuric acid and SPA mix that the substrate that will have silicon dioxide bar shaped mask pattern in this example is put into by volume ratio, and corrosion is 20 minutes under 300 ℃ of conditions.
Silicon dioxide or silicon nitride film are removed in step 4, corrosion, clean substrate, the sapphire graphical substrate 1 that obtains cleaning, the groove shape fringe period of this sapphire graphical substrate 1 platform and V-type is adjacent, be isosceles triangle not along the cross section of the V-shaped groove of sapphire [11-20] direction, two inclined-planes of V-shaped groove be the different crystal faces of 1-10k} family of crystal planes, wherein the minor face correspondence is＜1-102〉crystal face, and long limit correspondence is＜1-104 crystal face; Wherein the width of V-shaped groove is 1 to 50 μ m, and the degree of depth is 0.5 to 20 μ m, can have the platform of 0.5 to 50 μ m between two V-shaped grooves, also can not have platform and forms jagged groove; The Sapphire Substrate of this example after with wet etching rinsed well with deionized water, then this substrate put into by 15: 1 deionized water of volume ratio and the formulated solution of hydrofluoric acid, corrodes to remove silicon dioxide film in 30 seconds.Take out substrate at last, use a large amount of deionized water rinsings, thus the sapphire graphical substrate 1 that obtains cleaning, and Fig. 1 has provided the schematic cross-section of this sapphire graphical substrate 1.Groove on the sapphire graphical substrate 1 is V-shaped as can be seen, the periodic arrangement of V-shaped groove rule on substrate, each cycle is 7 μ m, the width of platform is about 3.2 μ m, the width of groove is about 3.8 μ m, and the V-shaped groove degree of depth is 2 μ m, and two limits are asymmetric, its minor face correspondence＜1-102〉crystal face, long limit correspondence＜1-104〉crystal face.
Step 5, directly adopt hydride gas-phase epitaxy system epitaxial growth GaN thick film 2 on resulting sapphire graphical substrate 1.In the hydride gas-phase epitaxy process, at first make GaN nucleation on the long limit of the V-shaped groove of sapphire graphical substrate 1 at first, and along direction growth perpendicular to the long limit of V-shaped groove, just along perpendicular to sapphire＜1-104〉the direction growth of crystal face, in the process of growth, constantly regulate growth parameter(s)s such as V/III, temperature, making that GaN thick film 2 is by at first along vertical sapphire＜1-104〉the direction growth of crystal face changes into gradually along sapphire C axle growth, finally obtains the unstressed GaN thick film 2 that the surface does not have crackle; Wherein on the sapphire graphical substrate 1 that contains the Asymmetric V-type groove of preparation, use the method epitaxial growth GaN thick film 2 of hydride gas-phase epitaxy, it is characterized in that, the control growing condition makes GaN begin most along the direction growth perpendicular to the long limit of V-shaped groove, and growth temperature is 600 to 1400 ℃; Wherein except selecting hydride gas-phase epitaxy method epitaxial growth GaN thick film 2 for use, can also select liquid phase epitaxy for use, metal organic vapor, the method epitaxial growth that the enclosure space gas phase transmits; Wherein select different substrates both can prepare polar GaN thick film 2, also can prepare various nonpolar and semi-polarity GaN thick films 2; Wherein GaN thick film 2 thickness are 1 μ m to 20mm; Adopt method epitaxial growth GaN thick film 2 on the sapphire graphical substrate 1 of preparation of hydride gas-phase epitaxy in this example.At first annealed 8 minutes in NH3 atmosphere, at high temperature grew then 1 hour, obtain the GaN thick film 2 of 100 μ m at last, GaN both had been grown in the platform place the most at first, also was grown on the long limit and minor face of V-shaped groove.But GaN is the fastest along the direction growth perpendicular to the long limit of V-shaped groove, thus Grown GaN on the minor face with Grown GaN on the platform all with long limit on Grown GaN merge mutually, and finally along direction growth perpendicular to the long limit of V-shaped groove.The GaN thick film 2 that adopts the method preparation is because the most at the beginning along the direction growth perpendicular to the long limit of V-shaped groove, and in growth course, merge gradually along different face Grown GaN, so GaN thick film 2 obtains effective relaxation, therefore can obtain stressless GaN thick film 2, thereby avoid the generation of crackle.
Unstressed GaN thick film 2 with preparation on the resulting sapphire graphical substrate 1 can prepare opto-electronic device, laser diode, photosensor or transistor; Can be in the no warpage that obtains on the sapphire graphical substrate 1, unstressed, flawless GaN thick film 2 without the direct required LED device architecture layer 3 of deposit on GaN thick film 2 of laser lift-off.
Embodiment 2
See also Fig. 2, present embodiment 2 is substantially the same manner as Example 1, and its difference is:
(1) adopt the photoetching process of standard on Sapphire Substrate, to make bar shaped earth silicon mask figure by lithography in the step 2 along [11-20] direction, standard technology such as this photoetching process comprises gluing, exposure, etching silicon dioxide, remove photoresist, the width of the earth silicon mask layer striped for preparing is 2 μ m, and the window area width is 5 μ m.
(2) after step 3 is finished, obtained the sapphire graphical substrate 1 of the cleaning different with example 1, the groove after the corrosion is V-shaped as can be seen, the periodic arrangement of V-shaped groove rule on substrate, and each cycle is 7 μ m.There is not platform between the V-shaped groove, sapphire graphical substrate 1 indentation.The V-shaped groove degree of depth is 3 μ m, and two limits are asymmetric, and its minor face correspondence＜1-102〉crystal face, long limit correspondence＜1-104〉crystal face.
(3) method of employing hydride gas-phase epitaxy epitaxial growth GaN thick film 2 on the sapphire graphical substrate 1 of preparation in the step 4.GaN only grows on the long limit of V-shaped groove the most at first, does not grow on the minor face, and Grown GaN mutually combines at last on the long limit of adjacent V-shaped groove.Adopt the method preparation GaN thick film 2 since nucleation just on the long limit of V-shaped groove, and in growth course on the adjacent V-shaped groove length limit Grown GaN mutually combine, so Stress Release is more complete, can access stressless GaN thick film 2.
(4) can prepare opto-electronic device, laser diode, photosensor or transistor with the unstressed GaN thick film for preparing on the resulting sapphire graphical substrate; Can be in the no warpage that obtains on the sapphire graphical substrate 1, unstressed, flawless GaN thick film 2 without the direct required LED device architecture layer 3 of deposit on GaN thick film 2 of laser lift-off.
Though the present invention discloses as above with embodiment; right its is not in order to limit the present invention; have in the technical field under any and know the knowledgeable usually; without departing from the spirit and scope of the present invention; when can doing a little change and retouching, so protection scope of the present invention is when looking being as the criterion that the claim scope defined.

Claims (10)

  1. One kind on the sapphire graphical substrate preparation unstressed GaN thick film method, may further comprise the steps:
    Step 1: deposit layer of silicon dioxide or silicon nitride film on the C surface sapphire substrate;
    Step 2: utilize conventional photoetching technique on the C of deposit silicon dioxide or silicon nitride film surface sapphire substrate, to make bar shaped silicon dioxide or silicon nitride mask graph by lithography along [11-20] direction;
    Step 3:, the bar shaped silicon dioxide or the silicon nitride mask graph of photoetching are transferred on the substrate by wet etching;
    Step 4: silicon dioxide or silicon nitride film are removed in corrosion, clean substrate, the sapphire graphical substrate that obtains cleaning;
    Step 5: directly adopt hydride gas-phase epitaxy system epitaxial growth GaN thick film on resulting sapphire graphical substrate, finish preparation.
  2. 2. the method that on the sapphire graphical substrate, prepares unstressed GaN thick film according to claim 1, wherein the surface of this sapphire graphical substrate is platform and V-shaped groove shape striped, and it is periodically adjacent, the cross section of this V-shaped groove is isosceles triangle not, this V-shaped groove is a window area, two inclined-planes of V-shaped groove be the different crystal faces of 1-10k} family of crystal planes, wherein the minor face correspondence is＜1-102〉crystal face, and long limit correspondence is＜1-104 crystal face.
  3. 3. the method for preparing unstressed GaN thick film on the sapphire graphical substrate according to claim 1, wherein the thickness of silicon dioxide or silicon nitride film is 10nm to 5 μ m.
  4. 4. the method that on the sapphire graphical substrate, prepares unstressed GaN thick film according to claim 1 and 2, wherein the width of fringe of bar shaped silicon dioxide or silicon nitride mask graph is 1 to 50 μ m, the window area width is 1 to 50 μ m.
  5. 5. according to claim 1 on the sapphire graphical substrate method of the unstressed GaN thick film of preparation, wherein wet etching is that sample after adopting sulfuric acid and phosphoric acid mixed liquor to photoetching carries out etching, etching temperature is 100-400 ℃.
  6. 6. the method for preparing unstressed GaN thick film on the sapphire graphical substrate according to claim 1, wherein substrate can also be from spinelle, GaN, AlN, GaAs, Si, SiC, LiAlO 2, LiGaO 2, ZrB 2Or HfB 2Select in the family that forms.
  7. 7. the method that on the sapphire graphical substrate, prepares unstressed GaN thick film according to claim 1, wherein the width of V-shaped groove is 1 to 50 μ m, the degree of depth is 0.5 to 20 μ m, is the platform of 0.5 to 50 μ m between two V-shaped grooves.
  8. 8. wherein there is not platform in the method for preparing unstressed GaN thick film on the sapphire graphical substrate according to claim 1 between two V-shaped grooves.
  9. 9. the method for preparing unstressed GaN thick film on the sapphire graphical substrate according to claim 1, wherein the temperature of growing GaN thick film is 600 to 1400 ℃.
  10. 10. the method that on the sapphire graphical substrate, prepares unstressed GaN thick film according to claim 1, wherein except selecting hydride gas-phase epitaxy method epitaxial growth GaN thick film for use, can also select liquid phase epitaxy for use, metal organic vapor, the method epitaxial growth that the enclosure space gas phase transmits.
CN2009102353350A 2009-09-30 2009-09-30 Method for preparing stress-free GaN thick film on sapphire patterned substrate Pending CN102034693A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104658887A (en) * 2015-01-12 2015-05-27 上海应用技术学院 Etching method for a-surface sapphire
CN109545933A (en) * 2018-11-08 2019-03-29 东南大学 A kind of nonpolar graphically AlN/ sapphire compound substrate and preparation method thereof
CN111739931A (en) * 2020-08-17 2020-10-02 南京中电芯谷高频器件产业技术研究院有限公司 Regrown GaN Schottky diode and manufacturing method thereof
WO2022165648A1 (en) * 2021-02-02 2022-08-11 华为技术有限公司 Patterned substrate for preparing gallium nitride substrate and method for preparing gallium nitride substrate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104658887A (en) * 2015-01-12 2015-05-27 上海应用技术学院 Etching method for a-surface sapphire
CN104658887B (en) * 2015-01-12 2017-08-25 上海应用技术学院 A kind of lithographic method of a surface sapphires
CN109545933A (en) * 2018-11-08 2019-03-29 东南大学 A kind of nonpolar graphically AlN/ sapphire compound substrate and preparation method thereof
CN111739931A (en) * 2020-08-17 2020-10-02 南京中电芯谷高频器件产业技术研究院有限公司 Regrown GaN Schottky diode and manufacturing method thereof
WO2022165648A1 (en) * 2021-02-02 2022-08-11 华为技术有限公司 Patterned substrate for preparing gallium nitride substrate and method for preparing gallium nitride substrate

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Application publication date: 20110427