University of Nebraska - Lincoln DigitalCommons@University of Nebraska - Lincoln Faculty Publications from the Department of Electrical & Computer Engineering, Department of Electrical and Computer Engineering 2019 GROWTH OF NITRIDE FILMS Yongfeng Lu University of Nebraska - Lincoln, [email protected] Hossein Rabiee Golgir Lincoln, NE Yunshen Zhou Lincoln, NE Follow this and additional works at: https://digitalcommons.unl.edu/electricalengineeringfacpub Part of the Computer Engineering Commons, and the Electrical and Computer Engineering Commons Lu, Yongfeng; Golgir, Hossein Rabiee; and Zhou, Yunshen, "GROWTH OF NITRIDE FILMS" (2019). Faculty Publications from the Department of Electrical and Computer Engineering. 496. https://digitalcommons.unl.edu/electricalengineeringfacpub/496 This Article is brought to you for free and open access by the Electrical & Computer Engineering, Department of at DigitalCommons@University of Nebraska - Lincoln. It has been accepted for inclusion in Faculty Publications from the Department of Electrical and Computer Engineering by an authorized administrator of DigitalCommons@University of Nebraska - Lincoln. US010233544B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 ,233 ,544 B2 Lu et al. (45 ) Date of Patent : Mar . 19 , 2019 ( 54 ) GROWTH OF NITRIDE FILMS HOIL 21/ 02378 ( 2013 .01 ) ; HOIL 21 /02381 ( 2013 . 01 ) ; HOIL 21 /02422 (2013 .01 ) (71 ) Applicant : Board of Regents of the University of (58 ) Field of Classification Search Nebraska , Lincoln , NE (US ) CPC . .. .. C23C 16 /34 ; C23C 16 / 303 ; C22C 11 /06 ; C22C 13 / 00 ; HOIL 21 /0254 ; HOLL (72 ) Inventors : Yongfeng Lu , Lincoln , NE (US ); 21/ 0262 ; HO1L 21/ 0242 ; HO1L 21 /02425 ; Hossein Rabiee Golgir , Lincoln , NE HO1L 21 /02422 ; HO1L 21 /02381 ; HOLL ( US ) ; Yunshen Zhou , Lincoln , NE 21/ 02378 ; H01L 29/ 2003 (US ) USPC . .. .. 428 /698 See application file for complete search history . (73 ) Assignee : NUtech Ventures, Lincoln , NE (US ) (56 ) References Cited ( * ) Notice : Subject to any disclaimer , the term of this patent is extended or adjusted under 35 U . S . PATENT DOCUMENTS U . S . C . 154 (b ) by 125 days . 2016 /0203972 Al * 7 /2016 Sundaram . .. .. HO1L 21/ 268 (21 ) Appl. No. : 15 / 158 ,305 257 / 76 (22 ) Filed : May 18 , 2016 OTHER PUBLICATIONS Prior Publication Data Bhuiyan et al. , “ Indium nitride (InN ) : A review on growth , char (65 ) acterization , and properties , ” Journal of Applied Physics , 2003 , US 2016 / 0340783 A1 Nov . 24 , 2016 94 ( 5 ) : 2779 - 2808 . Related U . S . Application Data (Continued ) (60 ) Provisional application No. 62/ 163, 663, filed on May Primary Examiner — William K Cheung 19 , 2015 . ( 74 ) Attorney, Agent, or Firm — Fish & Richardson P . C . (51 ) Int . CI. (57 ) ABSTRACT C23C 16 /34 ( 2006 .01 ) A gallium nitride thin film can be formed on a substrate at C22C 11 / 06 ( 2006 .01 ) a low temperature ( e . g ., not higher than 600° C .) by applying C22C 13 /00 ( 2006 .01 ) a laser to resonantly excite molecules of a first precursor that C23C 16 /48 ( 2006 .01 ) contains nitrogen , in which the laser has a wavelength that HOIL 21 /02 ( 2006 .01 ) is selected to match a vibration mode and / or a vibrational HOIL 29 /20 ( 2006 . 01 ) rotational mode of the molecules of the first precursor. A C23C 16 /30 ( 2006 .01 ) second precursor is provided in which the excited first (52 ) U .S . CI. precursor and the second precursor react to form a nitride CPC . C23C 16 /483 (2013 .01 ) ; C22C 11 / 06 that is deposited on the substrate . For example, the second ( 2013 . 01 ) ; C22C 13 / 00 ( 2013 . 01 ) ; C23C precursor may include gallium , and the nitride may be 16 / 303 (2013 .01 ) ; C23C 16 / 34 ( 2013 .01 ) ; gallium nitride. Other nitride films can be produced in a HOIL 21 /0242 ( 2013 .01 ) ; HOIL 21 / 0254 similar manner. ( 2013 . 01 ) ; HOIL 21 /0262 ( 2013 .01 ) ; HOIL 21/ 02425 (2013 .01 ) ; HOIL 29 /2003 ( 2013 .01 ) ; 91 Claims, 10 Drawing Sheets US 10 ,233 ,544 B2 Page 2 (56 ) References Cited OTHER PUBLICATIONS Elam et al. , “ Surface chemistry and film growth during TiN atomic layer deposition using TDMAT and NH3," Thin Solid Films, 2003, 436 ( 2 ) : 145 - 156 . Grandjean et al ., “ Molecular- beam epitaxy of gallium nitride on ( 0001) sapphire substrates using ammonia ,” Journal of Applied Physics, 1998 , 83 ( 3 ) : 1379 - 1383 . Keller and DenBaars, " Metalorganic chemical vapor deposition of group III nitridesa discussion of critical issues, ” Journal of Crystal Growth , 2003 , 248 : 479 - 486 . Molnar et al. , “Growth of gallium nitride by hydride vapor -phase epitaxy, ” Journal of Crystal Growth , 1997 , 178 ( 1 ) : 147 - 156 . Nagashima et al. , “ High - speed epitaxial growth of AlN above 1200° C . by hydride vapor phase epitaxy, ” Journal of Crystal Growth , 2007 , 300 ( 1 ) : 42 -44 . Ziegler et al ., “ Relationships between processing, microstructure and properties of dense and reaction -bonded silicon nitride, ” Jour nal of Materials Science, 1987 , 22 ( 9 ) : 3041 - 3086 . * cited by examiner UU. .S S .. Patent Patente meMar . 19te , 2019 mos Sheetmundiale 1 of 10 USus 10masu , 233 , 544 uB2 ys FIG . 1 122 140 FIG . 3 U . S . Patent Mar . 19 , 2019 Sheet 2 of 10 US 10 , 233 , 544 B2 126- Meter,128 NH3110 Power TMGa+N2 112130 Vacuum Pump,108 116 FIG.2 ._ _. 114 Heater,106 122- 136 DH 124mm Substrate,102 Stainlesssteelchamber,104 7122 ZnSewindow 134 _132 120- tunableCO2laser LookupTable Wavelength 138 Controller U . S . Patent Mar . 19 , 2019 Sheet 3 of 10 US 10 , 233 , 544 B2 W WWW ik 9.009GADOW -164 154- 09009QADOWE FIG.4C FIG.5C .. HiFi . unNeo substratem,Also 24: ME WWWW WWW MMMWWMWWWWMMMWMMW MMMM MMM —152 162 MMMMMMMM LMOCVD-600°C FIG.4B LMOCVD-60090 FIG.5B VINAW NMN MMM ALAMI WWWWWWWWW MVMMMMM MMMM MWM MMMM WWWMWM MWANAM Aljo,substrate MMM WIMWI unGio nm500OOS 500mm 150r -160 LMOCVD-250°C LMOCVD-250°C FIG.4A FIG.5A Also,substrate U . S . Patent Mar . 19 , 2019 Sheet 4 of 10 US 10 ,233 ,544 B2 90 80 182 MOCVD-600°C FIG.6A 70 170 60 20(deg.) FIG.6C 90 186 184 . 50 . .80 LMOCVD-250°C Al2O3(0006) 0002)Gan( 40 30 6070 10kr 8k 0 Al2O3(0006) 20(deg.) ) .u . a( Intensity XRD 174 90 50 Gan(0002) 80 40 LMOCVD-600°C 70 30 0 20001 20(deg.) FIG.6B ) .u . a( Intensity XRD 178 180)0006(Al2O3 5060 176- )0002(Gan 40 30 ). u. a ( Intensity XRD U . S . Patent Mar . 19 , 2019 Sheet 5 of 10 US 10 ,233 ,544 B2 200 202 Apply a first laser to resonantly excite molecules of a first precursor to produce at least one of nitrogen or nitrogen -associated species , in which the first laser has a wavelength that is selected to match a vibration mode of the molecules of the first precursor . Provide a second precursor having a component 204 that reacts with at least one of the nitrogen or the nitrogen - associated species to form a nitride , and cause the excited first precursor to react with the second precursor . 206 Deposit the nitride on a substrate . FIG . 7 atent Mar . 19 , 2019 Sheet 6 of 10 US 10 ,233 ,544 B2 210 212 Provide a substrate made of a material having a melting point less than 600 °C . Heat the substrate to a temperature that 214 is less than 600 °C . Apply a first laser to resonantly excite molecules of a 216 first precursor that contains nitrogen to produce at least one of nitrogen or nitrogen - associated species that reacts with a component of a second precursor to form a nitride , in which the first laser has a wavelength that is selected to match a vibration mode of the molecules of the first precursor . Deposit the nitride on the substrate . FIG . 8 U . S . Patent Mar . 19 , 2019 Sheet 7 of 10 US 10 , 233 , 544 B2 9000 198 * * 9.201um * *.' : 196- .: . 10.591um 1'.: wwww . 194(194 FIG.9 um719.10 192r 10.350um 190 9.219um U . S . Patent Mar . 19 , 2019 Sheet 8 of 10 US 10 , 233 , 544 B2 230wwwm 220 7226 2287 232 900 -9.219um -10.591um 224 -10.350um -9.201um -10.719um 222 Viewthissons.remporte nuANAONAMAPRIMA 800 . AY * Tu www. Ha . * $ * * ** * * * * matatineetWymiana NH,(A’-XB) Wavelength(nm) . Whet . AY2 FIG.10 www www mampuanunpamatkanman * * * NH(A'11-X*£) 300400500600700 +-*7 why .P A.VAA ' * - A . ***** 09€OV€_07€008087VO OH(A’e*-X?11) * 44 VAN * VM ) .u . a ( Intensity U . S . Patent Mar . 19 , 2019 Sheet 9 of 10 US 10 ,233 ,544 B2 PowerMeter, Precursor,112 NH3,110 126 128 Pump,108 104 V Vacuum Angle-3 FIG.11 248 244 Heater,106 246 Angle-2 242 Angle-1 Substrate,102 122 Window,124 134 132- 240 120 LASER Controller Lookup Table U . S . Patent Mar. 19 , 2019 Sheet 10 of 10 US 10 , 233 , 544 B2 J = 5 . 250 J = 4 .- -- - J = 3 .. ON . : : . : v = 1 ccaC - IIIIII - . pa wwwwwwwwwwwwwwww. 16.jeug J = 5 44444444444444* * * * * * * w J = 4 * w J = 3 wwwwwwwwwwwwwww . 1 = 0 by IIIIII NO T11:RRRRRRRRRRR P Branch 11 Q Branch LR Branch | FIG . 12 US 10 , 233 , 544 B2 GROWTH OF NITRIDE FILMS temperature notmore than 600° C . , in which the substrate is not subjected to more than 600° C . during deposition of the CROSS -REFERENCE TO RELATED nitride . In some examples , the method can include causing APPLICATION the excited first precursor to react with the second precursor, and maintaining the substrate at approximately 250° C . , in This application claims priority to U . S . provisional patent which the substrate is subjected no more than 260° C . during deposition of the nitride. In some examples, the method can application 62/ 163, 663 , filed on May 19 , 2015 , which is include causing the excited first precursor to react with the herein incorporated by reference in its entirety .