Source: http://www.google.com/patents/US8123859?dq=5,241,671
Timestamp: 2017-01-23 21:42:31
Document Index: 168592891

Matched Legal Cases: ['art 2', 'Application No. 2003303485', 'Application No. 2', 'Application No. 2', 'Application No. 02803675', 'Application No. 02806723', 'Application No. 02806723', 'Application No. 02806723', 'Application No. 02806723', 'Application No. 03808366', 'Application No. 06844804', 'Application No. 2003', 'Application No. 2003', 'Application No. 2003', 'Application No. 2003', 'Application No. 2004', 'Application No. 2004', 'Application No. 91137050', 'Application No. 03808366']

Patent US8123859 - Method and apparatus for producing large, single-crystals of aluminum nitride - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inPatentsA method and apparatus for producing bulk single crystals of AlN having low dislocation densities of about 10,000 cm−2 or less includes a crystal growth enclosure with Al and N2 source material therein, capable of forming bulk crystals. The apparatus maintains the N2 partial pressure at greater than...http://www.google.com/patents/US8123859?utm_source=gb-gplus-sharePatent US8123859 - Method and apparatus for producing large, single-crystals of aluminum nitrideAdvanced Patent SearchTry the new Google Patents, with machine-classified Google Scholar results, and Japanese and South Korean patents.Publication numberUS8123859 B2Publication typeGrantApplication numberUS 12/841,350Publication dateFeb 28, 2012Filing dateJul 22, 2010Priority dateDec 24, 2001Fee statusPaidAlso published asUS7776153, US20060005763, US20080006200, US20110011332Publication number12841350, 841350, US 8123859 B2, US 8123859B2, US-B2-8123859, US8123859 B2, US8123859B2InventorsLeo J. Schowalter, Glen A. Slack, J. Carlos RojoOriginal AssigneeCrystal Is, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (174), Non-Patent Citations (169), Referenced by (12), Classifications (19), Legal Events (2) External Links: USPTO, USPTO Assignment, EspacenetMethod and apparatus for producing large, single-crystals of aluminum nitride
19. The method of claim 2, wherein the thermal gradient is greater than 100°/cm.
An aspect of the invention includes an apparatus for the growth of bulk single crystal aluminum nitride. The apparatus includes a housing defining a growth chamber, the housing including a gas outlet configured for selectively evacuating and venting the growth chamber, a gas inlet configured for pressurizing the growth chamber, and a viewing port configured for pyrometric monitoring of crystal growth temperatures within the growth chamber. A radio frequency (rf) coil is disposed within the growth chamber and configured for inducing an electromagnetic field therein. A quartz tube is disposed coaxially within the coil. A first set of shielding is disposed coaxially within the quartz tube, including from about 5 to about 7 concentric pyrolytic boron nitride (pBN) cylinders, each of the pBN cylinders having a wall thickness of greater than about 0.05 inches (0.13 cm), each of the cylinders having a length dimension along the longitudinal axis greater than the length dimension of the coil. A second set of shielding is disposed coaxially within the first set of shielding, the second set of shielding including two concentric, open joint tungsten cylinders, each of the tungsten cylinders having a wall thickness of less than about 0.005 inches (0.013 cm); each of the tungsten cylinders having a length dimension along the longitudinal axis less than the length dimension of the rf coil. A push tube is disposed coaxially within the second set of shielding; the push tube having a proximal side and a distal side, the distal side including a set of metallic baffles having a center hole which provides for the pyrometric monitoring of crystal growth temperatures, the proximal side including another set of metallic baffles. A crucible is disposed coaxially within the push tube, the crucible having a conically shaped distal end and a proximal end; the crucible defining a crystal growth enclosure; the proximal end including a high purity, polycrystalline aluminum nitride source material, the distal end being configured for growth of the bulk single crystal aluminum nitride. The push tube is disposed on a push rod assembly configured for sliding the crucible and the push tube along the longitudinal axis. The first set of shielding and the second set of shielding are configured to provide a thermal gradient axially within the cavity of the crucible of greater than about 100° C./cm.
Another aspect of the invention includes a method for growing bulk single crystals of aluminum nitride. The method includes utilizing the apparatus described above, purging the growth chamber by evacuating the growth chamber to a pressure less than or equal to about 0.01 mbar (1 Pa), and refilling the growth chamber with substantially pure nitrogen gas to a pressure of about 1 bar (100 kPa). The growth chamber is then evacuated to a pressure less than or equal to about 0.01 mbar (1 Pa), and then pressurized to about 1 bar (100 kPa) with a gas including about 95% nitrogen and about 5% hydrogen. The chamber is heated to a first temperature, the heating including ramping the temperature of the conical upper end of the crucible to about 1800° C. in a period of about 15 minutes. The growth chamber is then pressurized to about 1.3 bar (130 kPa) with the gas including about 95% nitrogen and about 5% hydrogen, and heated to a growth temperature. A distal end of the crucible is then ramped to about 2200° C. in a period of about 5 hours. The push tube and the crucible are moved axially through the growth chamber at a rate of about 0.6 to about 0.9 millimeters per hour, wherein single crystals of aluminum nitride are grown.
A further aspect of the invention includes a method for growing bulk single crystals of aluminum nitride. The method includes evacuating a growth chamber, pressurizing the growth chamber to about 1 bar with a gas including about 95% nitrogen and about 5% hydrogen, and placing source polycrystalline AlN in a proximal end of a crystal growth enclosure. The method further includes placing a distal end of the crystal growth enclosure in a high temperature region of the growth chamber, ramping the high temperature region to about 1800° C., maintaining pressure in the growth chamber at about 1.3 bar, and ramping the high temperature region to about 2200° C. The distal end of the crystal growth enclosure is moved towards a low temperature region of growth chamber at a rate of about 0.6 to about 0.9 millimeters per hour, wherein a single crystal of aluminum nitride grows at the distal end of the crystal growth enclosure.
The present invention includes a method and apparatus for producing aluminum nitride (AlN) substrates that advantageously have a relatively small lattice mismatch (around 2.2%) with GaN, and have an almost identical thermal expansion from room temperature to 1000° C. Furthermore, AlN crystals grown by the present method have a low dislocation density of 10,000 cm−2 or less and may be grown to have a radial dimension exceeding 10 mm and a length exceeding 5 mm. These AlN crystals also advantageously have the same wurtzite (2H) crystal structure as GaN and nominally the same type of piezoelectric polarity. Also, the chemical compatibility with GaN is much better than that of the SiC. In addition, AlN substrates cut from the bulk crystals tend to be attractive for AlxGa1-xN devices requiring higher Al concentration (e.g., for high temperature, high power, radiation hardened, and ultra-violet (UV) wavelength applications).
Unfortunately, when the nitrogen pressure exceeds the stoichiometric partial pressure for a given partial pressure of aluminum (when stoichiometric, PN2=(½)PAl), mass transport of the Al, relative to the nitrogen gas, to the growing crystal surface is generally needed. Thus, at some point, the growth rate becomes limited by diffusion of Al atoms through the gas phase even though the surface kinetics would continue to predict increased crystal growth rate with increasing N2 pressure. Based on our current understanding of the surface kinetics involved, it has been found that this cross-over point is only slightly greater than 1 atmosphere for the growth geometry that was used by Slack and co-workers in the aforementioned Slack reference, and as shown in FIG. 1. However, during development of the present invention, it was found that this cross-over point is also dependent upon the diffusion lengths required for Al transport (which was approximately 2 to 5 cm in prior work). By reducing this (axial) length in embodiments of the present invention, which have been specifically configured to create a very sharp thermal profile in the work zone, it is has been found possible to significantly increase the growth rate relative to prior approaches.
Turning now to FIG. 1, the predicted AlN growth rate is shown as a function of N2 pressure. The curves labeled with squares and crosses show the growth rates assuming that it is limited by the diffusion of Al (for a 2.5 cm or 1 cm diffusion length, respectively) with no convection, while the third curve shows the predicted growth rate assuming that the growth rate is limited by the surface kinetics of nitrogen incorporation (ignoring gas-phase diffusion). The model assumes that the AlN source material is at 2300° C. while the growing crystal is maintained at 2200° C. These calculations also assume that the area of the evaporating surface and that of the growing crystal are equal and that diffusion effects may be neglected. This last assumption, as shown, ceases to be true at high enough N2 pressure. The cross-over point generally depends on the experimental geometry.
Embodiments of the present invention have demonstrated that the problem with diffusion described above can be circumvented, at least in part, by providing a net flow of gas from the source (11, FIG. 2) towards the growing crystal (7, FIG. 2) greater than that caused simply by the evaporation and recondensation process. This may be obtained when a thin wall tungsten crucible (9, FIG. 2) is used, and it may also be possible to obtain this effect with other crucible materials that are pervious to nitrogen gas, or with other types of selective barriers such as openings 20, 21, described hereinbelow with respect to FIGS. 3-5. Nitrogen is able to diffuse through thin-walled tungsten (W) crucibles at fairly high rates at the crystal growth temperatures (˜2300° C.) used. The diffusion rate of Al through the W walls is much lower. Thus, under equilibrium conditions, the partial pressure of nitrogen inside the crucible is identical to that outside (e.g., in chamber 2, FIG. 2) the crucible, while the total pressure of gasses inside the crucible may be higher due to the partial pressure of the Al vapor.
[Al]·[N]=K s, (3)
The value of FAlN is linear in ΔT for ΔT≦5100° C. We find that the linear dependence of FAlN on PN2 is valid (within 1%) between 0 and 200 bars of nitrogen gas for the experimentally determined values of EL and Ps in the temperature range 2000° C.<TH<2500° C. We have determined
A o(ΔT=50° C.,T H=2300° C.)=0.156 mm−hr−1−bar−1, (7)
using the data of Bolgar et al. (A. S. Bolgar, S. P. Gordienko, B. A. Ryklis, and V. V. Fesenko, in “Khim. Fiz. Nitridov”, p. 151-6 (1968) [Chem. Abstr. 71, 34003j (1969)]). for the Langmuir evaporation rate (259 mm/hr) and the equilibrium, stoichiometric nitrogen pressure determined from the JANAF tables (M. W. Chase et al. “JANAF Thermochemical Tables”, Third Edition (1985), see 0.1. Phys. Chem. Ref. Data 14, Supplement No. 1 (1985)), Ps(2300° C.)=0.13 bar. This equilibrium pressure would lead to an effective growth rate of 18.9 m/hr if all the nitrogen and aluminum stuck to the surface without re-evaporation and PAl=2PN2=Ps, such as shown in FIG. 1. These calculations assume that the area of the evaporating surface and that of the growing crystal are equal and that diffusion effects may be neglected. This last assumption is rather important and, as FIG. 1 shows, ceases to be true at high enough N2 pressure.
The observed growth rate in the Slack reference for TH=2300° C. and TC˜2200° C. run in 0.95 bar of N2 plus 0.05 bar of H2 was 0.3 mm/hr. This should be compared with the theoretically determined growth rate of 0.32 mm/hr. This is a remarkable agreement given the uncertainties in the experimental data for the Langmuir evaporation rate and in the measured growth rate by Slack and McNelly. Note that there are no adjustable parameters in the way that this theory was developed, the theory only depends on the experimentally determined equilibrium pressures and the measured Langmuir evaporation rates. Note also that the experiment was conducted in a crucible where the growing crystal surface was smaller than the evaporating AlN source material. This tends to lead to an amplification of the observed growth rate. It should also be noted that these equations predict a theoretical growth rate of 0.020 mm/hr at the stoichiometric nitrogen pressure (0.13 bar) at a source temperature of 2300° C. and a ΔT of 50° C.
An aspect of this invention is the arrangement of the shielding elements in the system that allows setting an adequate thermal gradient along the walls of push tube 3. As shown, there are two distinct sets of shielding elements around the push tube. The first set includes two concentric open joint tungsten cylinders 8, each having a thickness of less than about 0.005″ in a desired embodiment. The skilled artisan will recognize that other refractory metals such as molybdenum or rhenium may be substituted for W. The term ‘open-joint’ refers to the cylinders 8 having an open longitudinal seam (i.e., the cylinders to not extend a full 360 degrees) so that there is no continuous electrical path around the cylinder. This helps to prevent the cylinders from coupling to the rf fields and becoming too hot and/or absorbing power intended for heating the crucible. Both the open-joint and the thickness are chosen to minimize the coupling between these metallic parts and the 450 MHz rf electromagnetic field. In addition, cylinders 8 are preferably axially shorter than rf coil 6 and located nominally in the center of the coil 6 (e.g., both concentrically with coil 6 and equidistantly from both (axial) ends thereof) to avoid inducing local non-axial-symmetric hot spots on shields 8. The second set of shields 10 desirably include pyrrolitic boron nitride (pBN) cylinders (e.g., approximately five to seven cylinders, in particular embodiments), which in desirable embodiments, are at least 0.050 inches (1.3 mm) thick and several centimeters longer than rf coil 6. While a purpose of the pBN shields 10 is to thermally insulate the tube 3 to obtain the desire temperature in the work zone, the mission of the metallic shields 8 is two-fold. Shields 8 serve as heat reflectors causing the temperature in the center of the hot zone to be much higher than at the coil ends. In addition, they serve to protect the push tube 3 from picking up boron generated by the continuous sublimation of the pBN shields 10. (Boron has a eutectic point with tungsten at the growth temperatures used in this invention if the boron concentration exceeds some value. Once the boron picked up by the push tube is higher than that value, a liquid phase tends to form on the skin of the push tube leading to its failure.) The shielding arrangement described hereinabove advantageously produces a sharp thermal gradient on the crucible 9 (e.g., over 100° C./cm) as its tip 19 moves axially beyond the metallic shields 8. As discussed hereinabove, this relatively large gradient has been shown to facilitate large growth rates. As also shown, the shields 8, 10 may be enclosed in a dielectric tube (5) fabricated from quartz or other suitable material, to insulate the coil 6 from the metallic elements of the system and prevent arcing, etc. with them.
Ramp temperature of crucible tip to about 1800° C.
Crystal growth initially involves evacuating 30 the chamber 2 (FIG. 2). e.g., to pressures on the order of 0.01 mbar (1 Pa) using a vacuum pump. The chamber 2 is then refilled 32 with nitrogen gas. This step is preferably repeated 34 several times to minimize oxygen and moisture contamination. The chamber is then pressurized 36 to about 1 bar (100 kPa) with nitrogen gas which is preferably mixed with a small amount of hydrogen. For example, a gas including about 95-100% N2 and 0-5% H2 is useful. Exemplary embodiments use about 3% H2 and 97% N2 due to commercial availability of gas premixed at these percentages. Polycrystalline AlN source material 11 is placed 37 at a proximal end of crucible 9. The crucible 9 may then be evacuated and sealed, or may be provided with openings 20, 21 as described hereinabove. The crucible is then disposed 38 concentrically within tube 3, with tip 19 in the high temperature region of the furnace (i.e., nominally within the proximal end of shield 8). The temperature is then ramped 40 to bring the tip of the crucible to a temperature of approximately 1800° C., in particular embodiments, within about 15 minutes. At the end of this temperature ramp, the gas pressure is set and maintained 42 at a predetermined super-atmospheric pressure, and the temperature is ramped 44 to a final crystal growth temperature, e.g., in about 5 hours. During this ramping 44, the pressure is continuously adjusted 46, e.g., using a vent valve (not shown) to maintain it at that fixed value. The goal of this ramping 44 is to enhance the purity of the source material 11 by permitting part of the oxygen still contained within it to diffuse out of the crucible (e.g., through the crucible walls). This diffusion occurs because the vapor pressure of the aluminum suboxides (such as Al2O, AlO, etc.), generated due to the presence of oxygen in the source material, is known to be higher than that of Al over AlN for the same temperature.
FIG. 6 is a schematic cross-sectional view of a portion of a 260 nm laser diode fabricated using the method of the present invention. Initially, low defect density AlN substrate 40, which is prepared using the method discussed above, is polished by chemical mechanical polishing (CMP). Polished substrate 40 is then introduced into a conventional organo-metallic vapor phase epitaxy system (OMVPE). The surface of the low defect density AlN substrate is cleaned to remove any oxide or other impurities on the crystal surface. Cleaning is effected by heating the substrate at a temperature of 1150° C. for 20 min under ammonia plus nitrogen or hydrogen plus nitrogen flow prior to growth. An epitaxial layer 42 of AlN having a thickness of about 100 nm is then grown on substrate 40 to improve the surface quality of AlN substrate 40 before starting to grow the device layers. Next an undoped AlxGa1-xN buffer layer 44 having a thickness of approximately 1 μm is grown atop the epitaxial AlN layer 42 to relieve lattice mismatch through the formation of misfit dislocations. Formation of threading dislocations, which will continue to propagate through the device layers, is minimized by grading x from 0 to the final value of 0.5 (50% Al concentration). Onto buffer layer 44, a 1 μm thick layer 46 of Si-doped AlxGa1-xN (x=0.5) is grown. This layer 46 makes the n-type contact to the LD. A 50 nm thick layer 48 of Si-doped AlxGa1-xN (x=0.6) is then grown onto the Si-doped AlxGa1-xN (x=0.5) layer 46, followed by the growth of a 10 nm thick layer 50 of undoped AlxGa1-xN (x=0.5). Onto layer 50 is grown a 50 nm thick layer 52 of Mg-doped AlxGa1-xN (x=0.6) followed by the growth of a 1 μm thick layer 54 of Mg-doped AlxGa1-xN (x=0.5). After the growth steps, substrate 40 (now with epitaxial layers 42, 44, 46, 48, 50, 52 and 54 on it) is slowly ramped down from the growth temperature of about 1100° C. and removed from the OMVPE system. The top surface of epitaxial layer 54 is then coated with a metal contact layer 56 for the p-type semiconductor, and metal layer 56 is coated with a photoresist (not shown), which is then developed. The photoresist is removed where the n-type metal contact 58 will be formed. The substrate plus epitaxial layers plus metal layer are then etched such that the semiconductor is removed down to the n-type layer 46, which will be used for the n-type metal contact 58. A second coating of photoresist (for lift off) (not shown) is deposited, which is then patterned and removed where the n-type contacts are desired. The n-type metallization is complete, and the metal coating adjacent the second photoresist layer is removed by lift off to produce the desired wafer. Laser facets are achieved by cleaving the wafer. These facets may optionally be coated to protect them from damage. Wire bonding contacts (not shown) are made to the p-type and n-type metal layers and the laser diode is packaged appropriately.
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Growth, (Jan. 25, 2006), vol. 287, No. 2, pp. 372-375.Referenced byCiting PatentFiling datePublication dateApplicantTitleUS8344409 *Jul 7, 2011Jan 1, 2013Epistar CorporationOptoelectronic device and method for manufacturing the sameUS8946736Dec 31, 2012Feb 3, 2015Epistar CorporationOptoelectronic device and method for manufacturing the sameUS9028612Jun 30, 2011May 12, 2015Crystal Is, Inc.Growth of large aluminum nitride single crystals with thermal-gradient controlUS9070827Aug 14, 2013Jun 30, 2015Epistar CorporationOptoelectronic device and method for manufacturing the sameUS9299880Mar 13, 2014Mar 29, 2016Crystal Is, Inc.Pseudomorphic electronic and optoelectronic devices having planar contactsUS9299883Jan 28, 2014Mar 29, 2016Hexatech, Inc.Optoelectronic devices incorporating single crystalline aluminum nitride substrateUS9447519Apr 16, 2015Sep 20, 2016Crystal Is, Inc.Aluminum nitride bulk crystals having high transparency to untraviolet light and methods of forming themUS9447521Oct 22, 2014Sep 20, 2016Crystal Is, Inc.Method and apparatus for producing large, single-crystals of aluminum nitrideUS9525032Mar 26, 2014Dec 20, 2016Crystal Is, Inc.Doped aluminum nitride crystals and methods of making themUS9530940Jan 5, 2015Dec 27, 2016Epistar CorporationLight-emitting device with high light extractionUS20090250626 *Apr 3, 2009Oct 8, 2009Hexatech, Inc.Liquid sanitization deviceWO2015038398A1 *Sep 4, 2014Mar 19, 2015Nitride Solutions, Inc.Bulk diffusion crystal growth process* Cited by examinerClassifications U.S. Classification117/89, 117/105, 117/108, 117/942, 117/109International ClassificationH01L33/02, C30B29/04, H01L33/00, C30B11/00Cooperative ClassificationC30B29/403, H01L33/0075, C30B11/003, H01L33/025, C30B23/00, H01L2924/0002European ClassificationC30B29/40B, H01L33/00G3C, C30B23/00, C30B11/00FLegal EventsDateCodeEventDescriptionAug 31, 2010ASAssignmentOwner name: CRYSTAL IS, INC., NEW YORKFree format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SCHOWALTER, LEO J.;SLACK, GLEN A.;ROJO, J. 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