Method for synthesis of high quality large area bulk gallium based crystals
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C30B-007/10
C30B-025/02
C30B-029/40
출원번호
US-0988772
(2010-10-11)
등록번호
US-9175418
(2015-11-03)
국제출원번호
PCT/US2010/052175
(2010-10-11)
§371/§102 date
20110630
(20110630)
국제공개번호
WO2011/044554
(2011-04-14)
발명자
/ 주소
D'Evelyn, Mark P.
Speck, James S.
출원인 / 주소
Soraa, Inc.
대리인 / 주소
Saul Ewing LLP
인용정보
피인용 횟수 :
1인용 특허 :
112
초록▼
A large area nitride crystal, comprising gallium and nitrogen, with a non-polar or semi-polar large-area face, is disclosed, along with a method of manufacture. The crystal is useful as a substrate for a light emitting diode, a laser diode, a transistor, a photodetector, a solar cell, or for photoel
A large area nitride crystal, comprising gallium and nitrogen, with a non-polar or semi-polar large-area face, is disclosed, along with a method of manufacture. The crystal is useful as a substrate for a light emitting diode, a laser diode, a transistor, a photodetector, a solar cell, or for photoelectrochemical water splitting for hydrogen generation.
대표청구항▼
1. A method for forming a gallium based crystal, comprising: providing a bar-shaped proto-seed, the bar-shaped proto-seed comprising a gallium based crystal having a +c surface, a −c surface and at least one surface having a crystallographic orientation within 10 degrees of an a-plane {11-20} orient
1. A method for forming a gallium based crystal, comprising: providing a bar-shaped proto-seed, the bar-shaped proto-seed comprising a gallium based crystal having a +c surface, a −c surface and at least one surface having a crystallographic orientation within 10 degrees of an a-plane {11-20} orientation; andsubjecting the bar-shaped proto-seed to an ammonothermal growth process of a gallium based crystalline material to cause the proto-seed to grow inhomogeneously in at least one a-direction to form a gallium based crystal having at least one upper a-wing and at least one lower a-wing, wherein the upper a-wing comprises a +c surface and the upper a-wing and the lower a-wing are separated by a gap. 2. The method of claim 1, wherein the proto-seed has impurity concentrations of oxygen (O), hydrogen (H), carbon (C), sodium (Na), and potassium (K) below about 1×1017 cm−3, 2×1017 cm−3, 1×1017 cm3, 1×1016 cm−3, and 1×1016 cm−3, respectively. 3. The method of claim 1, wherein the upper a-wing is characterized by a dislocation density below 104 cm−2. 4. The method of claim 1, wherein each of the upper a-wing and the lower a-wing are characterized by a dislocation density below 104 cm−2. 5. The method of claim 1, wherein the proto-seed is provided by removing a seed crystal structure from a thick gallium and nitrogen containing substrate made using HVPE growth or wherein the proto seed is provided by removing a seed crystal structure from a thick gallium and nitrogen containing substrate made using ammonothermal growth. 6. The method of claim 1, further comprising separating at least one a-wing from the gallium based crystal and utilizing the separated a-wing as a seed crystal for ammonothermal crystal growth. 7. The method of claim 6, wherein the ammonothermal crystal growth produces a substantially rhombus-shaped gallium-based crystal with large-area c+ and c-surfaces with a surface area of at least 25 mm2, the rhombus-shaped crystal having a top surface and a bottom surface. 8. The method of claim 7, wherein the top and bottom surfaces of the substantially rhombus-shaped crystal have impurity concentrations of O, H, C, Na, and K between about 1×1017 cm−3 and 1×1019 cm−3, between about 1×1017 cm−3 and 2×1019 cm−3, below 1×1017 cm−3, below 1×1016 cm−3, and below 1×1016 cm−3, respectively. 9. The method of claim 7, wherein the top and bottom surfaces of the substantially rhombus-shaped crystal have impurity concentrations of O, H, C, and at least one of Na and K between about 1×1017 cm−3 and 1×1019 cm−3, between about 1×1017 cm3 and 2×1019 cm−3, below 1×1017 cm−3, and between about 3×1015 cm−3 and 1×1018 cm−3, respectively. 10. The method of claim 7, wherein the top and bottom surfaces of the substantially rhombus-shaped crystal have impurity concentrations of O, H, C, and at least one of F and Cl between about 1×1017 cm−3 and 1×1019 cm−3, between about 1×1017 cm−3 and 2×1019 cm−3, below 1×1017 cm−3, and between about 1×1015 cm−3 and 1×1017 cm−3, respectively. 11. The method of claim 7, wherein the substantially rhombus-shaped crystal has an infrared absorption peak at about 3175 cm−1, with an absorbance per unit thickness of greater than about 0.01 cm−1. 12. The method of claim 7, wherein the substantially rhombus-shaped crystal has a crystallographic radius of curvature greater than about 20 meters. 13. The method of claim 7, further comprising slicing the substantially rhombus-shaped crystal approximately parallel to a large area surface to form one or more wafers. 14. The method of claim 7, further comprising utilizing the substantially rhombus-shaped crystal or a wafer prepared therefrom as a seed crystal or substrate for further bulk crystal growth. 15. A method of manufacturing a semiconductor device, comprising utilizing a wafer prepared from the gallium-based crystal of claim 1 as a substrate for manufacture of a semiconductor structure, the semiconductor structure comprising at least one AlxInyGa(1-x-y) N epitaxial layer, where 0≦x, y, x+y≦1. 16. The method of claim 15, further comprising using the semiconductor structure in a gallium-nitride-based electronic device or optoelectronic device, the gallium-nitride-based electronic device or optoelectronic device being selected from a light emitting diode, a laser diode, a photodetector, an avalanche photodiode, a photovoltaic, a solar cell, a cell for photoelectrochemical splitting of water, a transistor, a rectifier, and a thyristor; one of a transistor, a rectifier, a Schottky rectifier, a thyristor, a p-i-n diode, a metal-semiconductor-metal diode, high-electron mobility transistor, a metal semiconductor field effect transistor, a metal oxide field effect transistor, a power metal oxide semiconductor field effect transistor, a power metal insulator semiconductor field effect transistor, a bipolar junction transistor, a metal insulator field effect transistor, a heterojunction bipolar transistor, a power insulated gate bipolar transistor, a power vertical junction field effect transistor, a cascade switch, an inner sub-band emitter, a quantum well infrared photodetector, a quantum dot infrared photodetector, or combinations thereof. 17. The method of claim 7, further comprising slicing the substantially rhombus-shaped crystal into at least two laterally-grown strip-shaped crystals with at least two long edges characterized by a surface orientation within about 10 degrees of an m-plane. 18. The method of claim 17, further comprising utilizing the laterally-grown strip-shaped crystals as seeds for ammonothermal crystal growth and growing the crystals by at least 5 mm in the +/−c direction to form a c-grown crystal. 19. A method of manufacturing a semiconductor device, comprising utilizing a wafer prepared the substantially rhombus-shaped crystal of claim 7 as a substrate for manufacture of a semiconductor structure, the semiconductor structure comprising at least one AlxInyGa(1-x-y)N epitaxial layer, where 0≦x, y, x+y≦1. 20. The method of claim 19, further comprising using the semiconductor structure in a gallium-nitride-based electronic device or optoelectronic device, the gallium-nitride-based electronic device or optoelectronic device being selected from a light emitting diode, a laser diode, a photodetector, an avalanche photodiode, a photovoltaic, a solar cell, a cell for photoelectrochemical splitting of water, a transistor, a rectifier, and a thyristor; one of a transistor, a rectifier, a Schottky rectifier, a thyristor, a p-i-n diode, a metal-semiconductor-metal diode, high-electron mobility transistor, a metal semiconductor field effect transistor, a metal oxide field effect transistor, a power metal oxide semiconductor field effect transistor, a power metal insulator semiconductor field effect transistor, a bipolar junction transistor, a metal insulator field effect transistor, a heterojunction bipolar transistor, a power insulated gate bipolar transistor, a power vertical junction field effect transistor, a cascade switch, an inner sub-band emitter, a quantum well infrared photodetector, a quantum dot infrared photodetector, or combinations thereof. 21. The method of claim 1, wherein the ammonothermal growth process includes the use of polycrystalline GaN material and a mineralizer comprising at least one of fluorine (F) and chlorine (Cl). 22. The method of claim 20, wherein the ammonothermal growth process is performed at a temperature of at least 650 degrees Celsius.
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