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Growth of GaN Nanocolumns and Their Coalescence Overgrowth Using Metalorganic Chemical vapor Deposition and the Characterization Study 以有機金屬氣相沉積法從事氮化鎵奈米柱生長和接合再生長以及其特性研究 研究生: 唐宗毅  (Tsung-Yi Tang) 指導教授: 楊志忠博士  (Dr. C. C. Yang)
Special Recognition ,[object Object],[object Object]
Acknowledgements ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Outline ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
[object Object],[object Object],Limiting Factors for the Nitride-based LED Development Threading dislocations
Methods of Reducing Threading Dislocation Density Epitaxial Lateral Overgrowth   APL  71 , 2639 (1997) Facet-controlled ELOG JCG 221, 316 (2000) Pendeoepitaxy APL  75 , 196 (1999)
Methods of Reducing Threading Dislocation Density Insertion of inter-mediate layer Patterned sapphire Insertion of LT AlN and SiN JAP  99 , 123518 (2006) Multiple insertions of SiN JAP  101 , 093502 (2007) Cantilever epitaxy APL  77 , 3233 (2000)
Motivations of the Research Reduction of residual strain and threading dislocation density Journal of Crystal Growth  287 , 500 (2006) Dislocation-free NCs Nano letters  6 , 1808 (2006) Strain-free NCs Jpn. J. Appl. Phys. Vol. 40 (2001)
Motivations of the Research ,[object Object],[object Object],[object Object],[object Object],[object Object],Threading dislocation Coalescence overgrowth of NC Substrate Overgrown thin film
Overview of Nitride Nanocolumn or Nanowire Growth with MBE ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
[object Object],[object Object],Overview of Nitride Nanocolumn or Nanowire Growth with MBE ,[object Object],[object Object]
Overview of Nitride Nanocolumn or Nanowire Growth with MBE Patterned growth with focused-ion-beam or electron-beam lithography  ---  K. Kishino et al.,  J. Cryst. Growth   311 , 2063 (2009). ---  S. Ishizawa et al.,  applied physics express   1 , 015006 (2008) Selective-Area Growth of GaN nanocolumns on Si(111) substrates using nitrided Al nanopatterns by rf-plasma-assisted molecular-beam epitaxy Ti-mask selective-area growth (SAG) by rf-plasma-assisted molecular beam epitaxy demonstrating extremely uniform GaN nanocolumn arrays
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Overview of Nitride Nanocolumn or Nanowire Growth with HVPE InGaN GaN
Overview of Nitride Nanocolumn or Nanowire Growth with VLS method ,[object Object],[object Object],phys. stat. sol. (b)  241 , 2775 (2004)  (111) MgO Nature materials 3, 524 (2004) J. Am Chem. Soc.123, 2793 (2001)
Overview of Nitride Nanocolumn or Nanowire Growth with MOCVD ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Nanotechnology  17 , 1454 (2006)
[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Overview of Nitride Nanocolumn or Nanowire Growth with MOCVD
Outline ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
MBE-grown GaN Nanocolumns Template Si (111) NCs (810 O C) AlN (710 O C) Column diameter: 100nm Column density: 10 9  /cm 2 Grown by Dr. Kent Averett
Growth Parameters of MOCVD-Overgrown GaN Pressure: 200 torr TMG flow rate: 17   mol/min NH 3  flow rate: 1000 sccm V/III ratio: 2600 Growth rate: 0.44 nm/sec Temperature: 800  O C, 900  O C, 1000  O C Thickness: 700 nm, 2.5   m Overgrown GaN NCs AlN Si
SEM and CL Images ,[object Object],[object Object],Growth temperature: 1000 O C, thickness: 2.5  m
Comparison between the Overgrown Sample and a GaN Thin Film (PL measurement) a high-quality GaN thin film   Substrate: sapphire FWHM of the peak of (0002) XRD curve: 190 arcsec FWHM of the peak of (10-12) XRD curve: 296 arcsec Thickness of GaN layer: 2-3  m The comparison shows that the overgrown sample has better optical quality than the GaN thin film. Wavelength (nm) Growth temperature: 1000 O C, thickness: 2.5  m
AFM and PL Measurements ,[object Object],[object Object],Growth temperature: 1000 O C, thickness: 2.5  m 20nm -20nm 0 0 2 4 6  m
Two-beam X-ray Diffraction   (Conventional Measurement) MOCVD overgrowth samples: A: 800  o C – 700 nm thick (1274 arcsec) B: 900  o C – 700 nm (1435) C1: 1000  o C – 700 nm (2653) C2: 1000  o C -- > 2.5   m (6245) Comparison samples: GaN1: good GaN film – 2   m (201) GaN2: poor GaN film – 2   m (1012) XRD results: courtesy of Wen-Yu Shiao (0002) plane
1  m 1  m Sample A Sample B Sample C1 Sample C2 Cross-section SEM Images
Three-beam Depth-dependent X-ray Diffraction Results Three-beam X-ray diffraction geometry Depth-dependent X-ray diffraction results c-axis C1 C2
Summary ,[object Object],[object Object],[object Object]
Outline ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
MOCVD Patterned Growth of GaN Nanocolumns 80nm SiO 2 Holes fabricated with nano-imprint lithography (courtesy of Epistar) GaN NCs maintain their geometry after they emerge from the growth mask if the growth conditions are changed into a pulsed MOCVD growth mode before the NCs emerge from the growth mask. Sapphire 2  m undoped GaN Sapphire 2  m undoped GaN time NH 3 TMGa Flow rate
Growth Conditions ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Growth Conditions ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],Four patterns are fabricated by nanoimprint lithography. The hole diameters of the four patterns are 250, 300, 450, and 600 nm, corresponding to center-to-center spacing sizes of 500, 600, 900, and 1200 nm, respectively.
Regularly Arranged GaN Nanocolumns - 1 Template hole diameter: 250 nm Hexagonal column size: ~300 nm Center-to-center spacing: 500 nm Clean NC bottom 1    m (a) (b) 100 nm SiO 2 SiO 2 250 nm (hole) 300 nm (column)
Hole diameter:   450 nm   Column diameter:   500nm  Separation:   900nm Hole diameter:   600 nm   Column diameter:   800nm  Separation:   1200nm Regularly Arranged GaN Nanocolumns - 2
Coalescence Overgrowth Results Hole diameter for column growth: 250 nm ,[object Object],[object Object],[object Object],(a) 1    m (b) 1    m I II III (c) SiO 2 SiO 2 SiO 2
CL and AFM Results 1   m Overgrown layer Nanocolumns Template Pit density: 2X10 7 cm -2 Roughness: 0.411nm AFM image 5   m*5  m Control sample Pit density: 3X10 8 cm -2 Roughness: 0.843nm Hole diameter: 250 nm Overgrown layer Template Nanocolumns 1   m
PL Measurements 10 K RT ,[object Object],[object Object],Hole diameter: 250 nm
Raman and XRD Measurements ,[object Object],[object Object],[object Object],Hole diameter: 250 nm
Comparisons of Internal Quantum efficiency Sample E: GaN template Samples A, B, C, D: NCs with hole sizes at 250, 300, 450, and 600 nm Samples AO, BO, CO,DO: Overgrowth samples with hole sizes at 250, 300, 450, and 600 nm NCs  Overgrown layers 10X 7X
Comparisons of Dislocation Density   Based on a depth-dependent X-ray diffraction measurement technique Edge and screw dislocation densities at the level of 10 7  cm -2  are achieved. The lateral domain size has been significantly increased. >10X >3X >3X
Comparison of Dislocation Density, Internal Quantum Efficiency, and Surface Roughness 0.81 6.63 x 10 8 1.09 x 10 8 1.1 0.834 E (GaN template) 1.71 1.32 x 10 8 9.81 x 10 7 1.6/3.9 0.665 DO/D (600 nm) 1.73 9.24 x 10 7 8.11 x 10 7 3.1/4.2 0.473 CO/C (450 nm) 2.01 6.21 x 10 7 5.09 x 10 7 4.1/7.1 0.425 BO/B (300 nm) 2.24 5.04 x 10 7 3.09 x 10 7 6.7/9.9 0.411 AO/A (250 nm) Lateral domain size (  m) Edge dislocation density (cm -2 ) Screw dislocation density (cm -2 ) IQE (%) Surface roughness (nm) Overgrowth sample
Cross-sectional TEM Images of Nanocolumns Threading dislocation is terminated at the bottom of a hole when the hole size is small. 250-nm hole size 450-nm hole size Two threading dislocations merge into one. Courtesy of Yung-Sheng Chen c-axis SiO 2 NC 100 nm template SiO 2 NC c-axis 200 nm template
Cross-sectional TEM Images of Overgrowth Samples New dislocations are formed on the masks when they are narrow. Such dislocations may disappear along overgrowth. 250-nm hole size 600-nm hole size Similar to ELOG 1 6 5 4 3 2 7 500 nm c-axis SiO 2 NC layer template overgrowth c-axis SiO 2 1   m NC layer overgrowth template 2 3 5 9 6 7 8 1 4 10
Edge effect due to different Thermal Expansion Coefficient ,[object Object],[object Object],mask Thin solid films  514 , 344 (2006)
Outline ,[object Object],[object Object],[object Object],[object Object],[object Object],[object Object],[object Object]
Sample Structures Sapphire Overgrown thin film 5 QWs 1   m 4  m nGaN/1  m uGaN Well:3nm Barrier: 15nm Undoped GaN Sapphire Overgrown thin film 5 QWs 120nm pGaN Undoped GaN Quantum well (QW) structure LED structure Conventional GaN template 2   m 5   m uGaN 80 nm SiO 2  mask Growth temperatures for blue and green emission are 715  O C and 675  O C, respectively. The growth temperature of barrier is 850  O C.
Blue LED Structure on Coalescence Overgrown GaN Template IQE A quick test shows ~80 % increase in output intensity. Scattering of the residual NC pattern may also help in enhancing light extraction. Wavelength: 460 nm 49.2% 20.1% ~80 % L-I curves
Green QW and LED on Coalescence Overgrown GaN Template 9.1 % increase IQE of green QW structure 14.1 % 10.4 % IQE of the green LED The reduction of dislocation density does not seem to significantly help in enhancing the efficiency of a green LED. The low miscibility between GaN and InN is the major cause for the low efficiency of a green LED.  Wavelength: 520 nm 21.2 % 12.4 %
Summary ,[object Object],[object Object],[object Object]
Conclusions ,[object Object],[object Object],[object Object]

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Oral Defense

  • 1. Growth of GaN Nanocolumns and Their Coalescence Overgrowth Using Metalorganic Chemical vapor Deposition and the Characterization Study 以有機金屬氣相沉積法從事氮化鎵奈米柱生長和接合再生長以及其特性研究 研究生: 唐宗毅 (Tsung-Yi Tang) 指導教授: 楊志忠博士 (Dr. C. C. Yang)
  • 2.
  • 3.
  • 4.
  • 5.
  • 6. Methods of Reducing Threading Dislocation Density Epitaxial Lateral Overgrowth APL 71 , 2639 (1997) Facet-controlled ELOG JCG 221, 316 (2000) Pendeoepitaxy APL 75 , 196 (1999)
  • 7. Methods of Reducing Threading Dislocation Density Insertion of inter-mediate layer Patterned sapphire Insertion of LT AlN and SiN JAP 99 , 123518 (2006) Multiple insertions of SiN JAP 101 , 093502 (2007) Cantilever epitaxy APL 77 , 3233 (2000)
  • 8. Motivations of the Research Reduction of residual strain and threading dislocation density Journal of Crystal Growth 287 , 500 (2006) Dislocation-free NCs Nano letters 6 , 1808 (2006) Strain-free NCs Jpn. J. Appl. Phys. Vol. 40 (2001)
  • 9.
  • 10.
  • 11.
  • 12. Overview of Nitride Nanocolumn or Nanowire Growth with MBE Patterned growth with focused-ion-beam or electron-beam lithography --- K. Kishino et al., J. Cryst. Growth 311 , 2063 (2009). --- S. Ishizawa et al., applied physics express 1 , 015006 (2008) Selective-Area Growth of GaN nanocolumns on Si(111) substrates using nitrided Al nanopatterns by rf-plasma-assisted molecular-beam epitaxy Ti-mask selective-area growth (SAG) by rf-plasma-assisted molecular beam epitaxy demonstrating extremely uniform GaN nanocolumn arrays
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  • 18. MBE-grown GaN Nanocolumns Template Si (111) NCs (810 O C) AlN (710 O C) Column diameter: 100nm Column density: 10 9 /cm 2 Grown by Dr. Kent Averett
  • 19. Growth Parameters of MOCVD-Overgrown GaN Pressure: 200 torr TMG flow rate: 17  mol/min NH 3 flow rate: 1000 sccm V/III ratio: 2600 Growth rate: 0.44 nm/sec Temperature: 800 O C, 900 O C, 1000 O C Thickness: 700 nm, 2.5  m Overgrown GaN NCs AlN Si
  • 20.
  • 21. Comparison between the Overgrown Sample and a GaN Thin Film (PL measurement) a high-quality GaN thin film Substrate: sapphire FWHM of the peak of (0002) XRD curve: 190 arcsec FWHM of the peak of (10-12) XRD curve: 296 arcsec Thickness of GaN layer: 2-3  m The comparison shows that the overgrown sample has better optical quality than the GaN thin film. Wavelength (nm) Growth temperature: 1000 O C, thickness: 2.5  m
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  • 23. Two-beam X-ray Diffraction (Conventional Measurement) MOCVD overgrowth samples: A: 800 o C – 700 nm thick (1274 arcsec) B: 900 o C – 700 nm (1435) C1: 1000 o C – 700 nm (2653) C2: 1000 o C -- > 2.5  m (6245) Comparison samples: GaN1: good GaN film – 2  m (201) GaN2: poor GaN film – 2  m (1012) XRD results: courtesy of Wen-Yu Shiao (0002) plane
  • 24. 1  m 1  m Sample A Sample B Sample C1 Sample C2 Cross-section SEM Images
  • 25. Three-beam Depth-dependent X-ray Diffraction Results Three-beam X-ray diffraction geometry Depth-dependent X-ray diffraction results c-axis C1 C2
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  • 28. MOCVD Patterned Growth of GaN Nanocolumns 80nm SiO 2 Holes fabricated with nano-imprint lithography (courtesy of Epistar) GaN NCs maintain their geometry after they emerge from the growth mask if the growth conditions are changed into a pulsed MOCVD growth mode before the NCs emerge from the growth mask. Sapphire 2  m undoped GaN Sapphire 2  m undoped GaN time NH 3 TMGa Flow rate
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  • 31. Regularly Arranged GaN Nanocolumns - 1 Template hole diameter: 250 nm Hexagonal column size: ~300 nm Center-to-center spacing: 500 nm Clean NC bottom 1  m (a) (b) 100 nm SiO 2 SiO 2 250 nm (hole) 300 nm (column)
  • 32. Hole diameter: 450 nm Column diameter: 500nm Separation: 900nm Hole diameter: 600 nm Column diameter: 800nm Separation: 1200nm Regularly Arranged GaN Nanocolumns - 2
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  • 34. CL and AFM Results 1  m Overgrown layer Nanocolumns Template Pit density: 2X10 7 cm -2 Roughness: 0.411nm AFM image 5  m*5  m Control sample Pit density: 3X10 8 cm -2 Roughness: 0.843nm Hole diameter: 250 nm Overgrown layer Template Nanocolumns 1  m
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  • 37. Comparisons of Internal Quantum efficiency Sample E: GaN template Samples A, B, C, D: NCs with hole sizes at 250, 300, 450, and 600 nm Samples AO, BO, CO,DO: Overgrowth samples with hole sizes at 250, 300, 450, and 600 nm NCs Overgrown layers 10X 7X
  • 38. Comparisons of Dislocation Density Based on a depth-dependent X-ray diffraction measurement technique Edge and screw dislocation densities at the level of 10 7 cm -2 are achieved. The lateral domain size has been significantly increased. >10X >3X >3X
  • 39. Comparison of Dislocation Density, Internal Quantum Efficiency, and Surface Roughness 0.81 6.63 x 10 8 1.09 x 10 8 1.1 0.834 E (GaN template) 1.71 1.32 x 10 8 9.81 x 10 7 1.6/3.9 0.665 DO/D (600 nm) 1.73 9.24 x 10 7 8.11 x 10 7 3.1/4.2 0.473 CO/C (450 nm) 2.01 6.21 x 10 7 5.09 x 10 7 4.1/7.1 0.425 BO/B (300 nm) 2.24 5.04 x 10 7 3.09 x 10 7 6.7/9.9 0.411 AO/A (250 nm) Lateral domain size (  m) Edge dislocation density (cm -2 ) Screw dislocation density (cm -2 ) IQE (%) Surface roughness (nm) Overgrowth sample
  • 40. Cross-sectional TEM Images of Nanocolumns Threading dislocation is terminated at the bottom of a hole when the hole size is small. 250-nm hole size 450-nm hole size Two threading dislocations merge into one. Courtesy of Yung-Sheng Chen c-axis SiO 2 NC 100 nm template SiO 2 NC c-axis 200 nm template
  • 41. Cross-sectional TEM Images of Overgrowth Samples New dislocations are formed on the masks when they are narrow. Such dislocations may disappear along overgrowth. 250-nm hole size 600-nm hole size Similar to ELOG 1 6 5 4 3 2 7 500 nm c-axis SiO 2 NC layer template overgrowth c-axis SiO 2 1  m NC layer overgrowth template 2 3 5 9 6 7 8 1 4 10
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  • 44. Sample Structures Sapphire Overgrown thin film 5 QWs 1  m 4  m nGaN/1  m uGaN Well:3nm Barrier: 15nm Undoped GaN Sapphire Overgrown thin film 5 QWs 120nm pGaN Undoped GaN Quantum well (QW) structure LED structure Conventional GaN template 2  m 5  m uGaN 80 nm SiO 2 mask Growth temperatures for blue and green emission are 715 O C and 675 O C, respectively. The growth temperature of barrier is 850 O C.
  • 45. Blue LED Structure on Coalescence Overgrown GaN Template IQE A quick test shows ~80 % increase in output intensity. Scattering of the residual NC pattern may also help in enhancing light extraction. Wavelength: 460 nm 49.2% 20.1% ~80 % L-I curves
  • 46. Green QW and LED on Coalescence Overgrown GaN Template 9.1 % increase IQE of green QW structure 14.1 % 10.4 % IQE of the green LED The reduction of dislocation density does not seem to significantly help in enhancing the efficiency of a green LED. The low miscibility between GaN and InN is the major cause for the low efficiency of a green LED. Wavelength: 520 nm 21.2 % 12.4 %
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