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Fabrication and characterization of one-dimensional solid-state model systems on silicon

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Fabrication and characterization of one-dimensional solid-state model systems on silicon

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  1. 1. Fabrication & Characterization of 1D Solid-State Model Systems on Silicon FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS François Bianco
  2. 2. Fabrication & Characterization of 1D Nanolines on Silicon FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS François Bianco
  3. 3. Motivations
  4. 4. Time Moore's Conjecture "The number of transistors incorporated in a chip will approximately double every 24 months." Gordon Moore, Intel co-founder 108 104 106 Numberoftransistors
  5. 5. Time Moore's Conjecture "The number of transistors incorporated in a chip will approximately double every 24 months." Gordon Moore, Intel co-founder 108 104 106 Numberoftransistors Pictures, CC-BY-SA Wikipedia contributors 1980 2010
  6. 6. Size Limit mm ŵm øhairs nm 1947 2012 © Intel newsroom 3D transistor & Nature Nanotechnology 7, 242 (2012) cells
  7. 7. Size Limit mm ŵm øhairs nm 1947 2012 © Intel newsroom 3D transistor & Nature Nanotechnology 7, 242 (2012) cells "What would happen if we could arrange the atoms one by one the way we want them?" Richard Feynman
  8. 8. Chain, CC-BY BotheredByBees (Flickr) Atom Chains or nanolines/nanowires
  9. 9. Nanowire's Applications Nature Photonics 7, 306 (2013) Adv. Mater. (2013) Adv. Mater. 15, 997 (2003) Angew. Chem. 120, 4597 (2008) APL 85, 6389 (2004) Nature Nanotechnol. 2, 626 (2007) Nature Nanotechnol. 7, 242 (2012) Memory Single-atom transistor Solar cell Gas detector Catalyst Vertical nanowires, © EPFL Press Nature Biotechnol. 23, 1294 (2005) Proteins detector
  10. 10. Open Questions Fabrication? Properties? Lego bricks, CC-BY-SA dbesham (Flickr)
  11. 11. Presentation Outline Physics in One Dimension ? Measurement & Synthesis of Nanolines Nanolines on Silicon: Bi nanolines Haiku stripes Haiku Dangling Bond Rows
  12. 12. Physics in One Dimension One-dimensional CC-BY-NC-ND (with permission) Andredoreto (Flickr)
  13. 13. One Dimension Trac Jam,, CC-BY-SA Andreas (Flickr)
  14. 14. 1D Physics CC-BY-NC-ND (with permissions) Water drop, Beauty Eye & Pipes, e.asphyx (Flickr) Fermi Liquid Tomonaga-Luttinger Liquid 2D 1D Quasiparticles Collective excitations
  15. 15. 1D Physics CC-BY-NC-ND (with permissions) Water drop, Beauty Eye & Pipes, e.asphyx (Flickr) Fermi Liquid Tomonaga-Luttinger Liquid 2D 1D Quasiparticles Collective excitations Spin-charge separation Power laws Peierls distortion Predictions:
  16. 16. a 2a Peierls Distortion Energie EF -π/2a π/2a Energie EF -π/2a π/2a Wavevector Wavevector Insulator Metallic
  17. 17. Peierls Distortion Example 293 K (20°C) 4.7 K (-268°C) Insulator Platinium on Ge(001) Surf. Sci. 602, 1731 (2008) Metallic
  18. 18. Can We See Nanostructures?
  19. 19. Scanning Pr e Braille, CC-BY-SA kainita (Flickr) I Feedback Scanning tunneling microscope (STM)
  20. 20. 2 nm Monohydride Silicon (001) Scanning Probe I Feedback Scanning tunneling microscope (STM)
  21. 21. STM Laboratory Low Temperature 77 K (­196°C) Ultra-High Vacuum (UHV, ~ 5×10-11 mbar)
  22. 22. Nanolines S nt es s ❚❤e ❯n✐✈ersa❧ ▲a❜e❧✱ ❈❈✲❇❨✲N❈ ❘an❞a❧❧ ▼unroe ✭❳❑❈❉ n➦✶✶✷✸✮
  23. 23. Fabrication Methods Top-down (Lithography)
  24. 24. Fabrication Methods Top-down (Lithography) Bottom-up (Self-assembly)
  25. 25. ❱icinal Surfaces Stairs, courtesy Sylvain Masson (Flickr)
  26. 26. Vici♥al Surfaces ❙tairs, courtes② ❙②l ai✁ Masso✁ (❋lic❦r) Co o✂ ✄ici✂al Cu(111) €☎✆ ✽7, 16✹06(☎) (✝01✞)
  27. 27. 2 nm dim er row [110] [110] Buckled c(4×2) Flip-flop (2×1) Silicon (001) Buckled c(4×2) Flip-flop (2×1) SideviewTopviewSideviewTopview
  28. 28. Synthesis Principle
  29. 29. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr)
  30. 30. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr) Bismuth Bismuth, Free Art Alchemist-hp (Wikipedia)
  31. 31. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr) Bismuth Bismuth, Free Art Alchemist-hp (Wikipedia) Rows of Red, CC-BY-NC-ND (with permission) sea turtle (Flickr) 580°C
  32. 32. Bismut Nano nes
  33. 33. Con tant Width ✺n♠ 2 n♠ 4 ✟i di✠❡r✡ wid❡☛o✉☞✌❡ ❝hain o❢ ✍i di✠❡r✡
  34. 34. Tunable Density 20 nm Low High
  35. 35. Micro✎eters Long 1 μm 50 nm ❩oo✏
  36. 36. sideviewtopview Haiku Structure BiBi 5 7 5 7 5 J.H.G Owen et al. J. Mater. Sci. 41, 4568 (2006) Si
  37. 37. Bi-Nanolines Advantages Self-assembled Micrometers long Tunable density Potential template Well know structure On a semiconductor Flat surface Fixed width
  38. 38. Haiku Stripes Appl. Phys. Lett. 97, 093102 (2010) & Phys. Rev. B 84, 35328 (2011)
  39. 39. Synthesis Hydrogenation 380°C
  40. 40. sideview 2 nm ✑onoh✒✓ri✓e Silicon H H H H
  41. 41. 10 nm 1 nm Haiku Stripes
  42. 42. Hai✔u ✕tripe ✖o✗✘✙ ✚i✚i ✛ i ✜ e ✢ iew 5 7 5 7 5 ✣i
  43. 43. Haiku Stripe Model ✤ i ✥ e ✦ iew 5 7 5 7 5 H H H H H H Si
  44. 44. Haiku Stripe Model sideview 5 7 5 7 5 H H H H H H Si Field, CC-BY-SA skrewtape (Flickr)
  45. 45. Haiku Stripe Model sideview 5 7 5 7 5 H H H H H H Si Field, CC-BY-SA skrewtape (Flickr) Bulbs, CC-BY-SA, brewbooks (Flickr)
  46. 46. How can we be sure that it is a silicon only structure?
  47. 47. X-Ray Photospectroscopy Eγ X-ray e- Ekin Spectrometer Ekin Eγ Core levels Valence band Φ e- Binding energy (XPS)
  48. 48. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal
  49. 49. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi
  50. 50. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi Bi-exposed sample after H exposure
  51. 51. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi Bi-exposed sample after H exposure
  52. 52. STM Simulations In collaboration with Prof. D. Bowler UCL & LCN Relaxed structure STM simulation Charges densities
  53. 53. 1 nm Filled States simulation experiment High current (200 pA) simulation experiment Low current (80 pA)
  54. 54. simulation experiment Cross Section 1.54 nm 70pm 5 pm Height Width simulation oset -10 pm experiment 1 nm
  55. 55. Empty States +2.5 V Simulations + 2.5 eV Data
  56. 56. Empty States +2.5 V Simulations + 2.5 eV Data 3 nm +2.0 V 1 nm + 1.0 eV
  57. 57. Charge Densities 3 nm Sideview
  58. 58. What else?
  59. 59. Air Resistant Exposed to air for 25 min 3 nm
  60. 60. Micrometer Long 200 nm 50 nm
  61. 61. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air
  62. 62. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air Delocalized electronic state Perfectly matching model
  63. 63. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air Delocalized electronic state Perfectly matching model Contacting Probing 1D physics &
  64. 64. What about Physics? Contacting Electrode Clamp Silicon 1 mm Mask deposition
  65. 65. 20 nm Markers & Contacts APL 100, 103103 (2012) Au markers Gold depositionExample
  66. 66. Optical measurement Doping Spectroscopy I(+1.5 V) What about Physics? 2 nm Outlook:
  67. 67. 1D Dan l n Bon s Rows ❆✧★ ◆ano (2013)
  68. 68. Hydrog✩nation 42✵✪✫ Synthesis
  69. 69. Assemb✬y Interests Molecular molds Atom assembly Annu. Rev. Phys. Chem. 60, 193 (2009) PRL 91, 136104 (2003) Gallium Phosphine Both examples were sequentially made
  70. 70. Haiku DB ✯ows H H π* π sideview Hydrogenated Si dimer Dangling Bond (DB)
  71. 71. 10 n H✰B Rehydrogenated
  72. 72. Central Dimer Model✳3DviewSideview H H H H Buckled Flat H H H H
  73. 73. H Binding Energy H atom on Si(001) 4.37 eV +0.16 +0.13 -0.10 -0.15 + - More stable Less stable EB/H[eV] sideview H H H H Buckled Flat H H H H -0.15 +0.13 -0.10 +0.16 From DFT calculations
  74. 74. Missing Hydrogen6% Si terraces % of dehydrogenated Si atoms
  75. 75. Missing Hydrogen6% Si terraces % of dehydrogenated Si atoms85% Haiku stripe
  76. 76. Alternating Flat Dimers + 1.8 V - 1.8 V
  77. 77. Alternating Flat Dimers + 1.8 V - 1.8 V Spin-polarized structure? Test at room temperature Outlook:
  78. 78. Properties Summary Micrometer long Highly reactive template Self-assembled Known structure
  79. 79. Properties Summary Micrometer long Highly reactive template Self-assembled Known structure Assembling 1D molecular or atomic chains
  80. 80. Con l s on
  81. 81. ✴✻mmary Self-assembly Lego bricks, CC-BY-SA dbesham (Flickr) Haiku stripes Haiku DB rows Bismuth nanolines
  82. 82. Summary Haiku stripes Haiku DB rows
  83. 83. FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS ✼✾anks & ❏❛✿❀s ❁●❁❖we❂❃❄❣❅❊❂❍❁■öster ◗❲oup photo, ➞❬❭❪❫❴❵❥♦s
  84. 84. "Atomic hashi. A pair of Bismuth dimers, On Silicon core. Remove all Bismuth, Silicon in silicon. Atomic template." James H.G. Owen 5 7 5 7 5 H H H H H H Si
  1. 1. Fabrication & Characterization of 1D Solid-State Model Systems on Silicon FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS François Bianco
  2. 2. Fabrication & Characterization of 1D Nanolines on Silicon FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS François Bianco
  3. 3. Motivations
  4. 4. Time Moore's Conjecture "The number of transistors incorporated in a chip will approximately double every 24 months." Gordon Moore, Intel co-founder 108 104 106 Numberoftransistors
  5. 5. Time Moore's Conjecture "The number of transistors incorporated in a chip will approximately double every 24 months." Gordon Moore, Intel co-founder 108 104 106 Numberoftransistors Pictures, CC-BY-SA Wikipedia contributors 1980 2010
  6. 6. Size Limit mm ŵm øhairs nm 1947 2012 © Intel newsroom 3D transistor & Nature Nanotechnology 7, 242 (2012) cells
  7. 7. Size Limit mm ŵm øhairs nm 1947 2012 © Intel newsroom 3D transistor & Nature Nanotechnology 7, 242 (2012) cells "What would happen if we could arrange the atoms one by one the way we want them?" Richard Feynman
  8. 8. Chain, CC-BY BotheredByBees (Flickr) Atom Chains or nanolines/nanowires
  9. 9. Nanowire's Applications Nature Photonics 7, 306 (2013) Adv. Mater. (2013) Adv. Mater. 15, 997 (2003) Angew. Chem. 120, 4597 (2008) APL 85, 6389 (2004) Nature Nanotechnol. 2, 626 (2007) Nature Nanotechnol. 7, 242 (2012) Memory Single-atom transistor Solar cell Gas detector Catalyst Vertical nanowires, © EPFL Press Nature Biotechnol. 23, 1294 (2005) Proteins detector
  10. 10. Open Questions Fabrication? Properties? Lego bricks, CC-BY-SA dbesham (Flickr)
  11. 11. Presentation Outline Physics in One Dimension ? Measurement & Synthesis of Nanolines Nanolines on Silicon: Bi nanolines Haiku stripes Haiku Dangling Bond Rows
  12. 12. Physics in One Dimension One-dimensional CC-BY-NC-ND (with permission) Andredoreto (Flickr)
  13. 13. One Dimension Trac Jam,, CC-BY-SA Andreas (Flickr)
  14. 14. 1D Physics CC-BY-NC-ND (with permissions) Water drop, Beauty Eye & Pipes, e.asphyx (Flickr) Fermi Liquid Tomonaga-Luttinger Liquid 2D 1D Quasiparticles Collective excitations
  15. 15. 1D Physics CC-BY-NC-ND (with permissions) Water drop, Beauty Eye & Pipes, e.asphyx (Flickr) Fermi Liquid Tomonaga-Luttinger Liquid 2D 1D Quasiparticles Collective excitations Spin-charge separation Power laws Peierls distortion Predictions:
  16. 16. a 2a Peierls Distortion Energie EF -π/2a π/2a Energie EF -π/2a π/2a Wavevector Wavevector Insulator Metallic
  17. 17. Peierls Distortion Example 293 K (20°C) 4.7 K (-268°C) Insulator Platinium on Ge(001) Surf. Sci. 602, 1731 (2008) Metallic
  18. 18. Can We See Nanostructures?
  19. 19. Scanning Pr e Braille, CC-BY-SA kainita (Flickr) I Feedback Scanning tunneling microscope (STM)
  20. 20. 2 nm Monohydride Silicon (001) Scanning Probe I Feedback Scanning tunneling microscope (STM)
  21. 21. STM Laboratory Low Temperature 77 K (­196°C) Ultra-High Vacuum (UHV, ~ 5×10-11 mbar)
  22. 22. Nanolines S nt es s ❚❤e ❯n✐✈ersa❧ ▲a❜e❧✱ ❈❈✲❇❨✲N❈ ❘an❞a❧❧ ▼unroe ✭❳❑❈❉ n➦✶✶✷✸✮
  23. 23. Fabrication Methods Top-down (Lithography)
  24. 24. Fabrication Methods Top-down (Lithography) Bottom-up (Self-assembly)
  25. 25. ❱icinal Surfaces Stairs, courtesy Sylvain Masson (Flickr)
  26. 26. Vici♥al Surfaces ❙tairs, courtes② ❙②l ai✁ Masso✁ (❋lic❦r) Co o✂ ✄ici✂al Cu(111) €☎✆ ✽7, 16✹06(☎) (✝01✞)
  27. 27. 2 nm dim er row [110] [110] Buckled c(4×2) Flip-flop (2×1) Silicon (001) Buckled c(4×2) Flip-flop (2×1) SideviewTopviewSideviewTopview
  28. 28. Synthesis Principle
  29. 29. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr)
  30. 30. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr) Bismuth Bismuth, Free Art Alchemist-hp (Wikipedia)
  31. 31. Synthesis Principle Seeds, CC-BY-NC-SA CIMMYT (Flickr) Bismuth Bismuth, Free Art Alchemist-hp (Wikipedia) Rows of Red, CC-BY-NC-ND (with permission) sea turtle (Flickr) 580°C
  32. 32. Bismut Nano nes
  33. 33. Con tant Width ✺n♠ 2 n♠ 4 ✟i di✠❡r✡ wid❡☛o✉☞✌❡ ❝hain o❢ ✍i di✠❡r✡
  34. 34. Tunable Density 20 nm Low High
  35. 35. Micro✎eters Long 1 μm 50 nm ❩oo✏
  36. 36. sideviewtopview Haiku Structure BiBi 5 7 5 7 5 J.H.G Owen et al. J. Mater. Sci. 41, 4568 (2006) Si
  37. 37. Bi-Nanolines Advantages Self-assembled Micrometers long Tunable density Potential template Well know structure On a semiconductor Flat surface Fixed width
  38. 38. Haiku Stripes Appl. Phys. Lett. 97, 093102 (2010) & Phys. Rev. B 84, 35328 (2011)
  39. 39. Synthesis Hydrogenation 380°C
  40. 40. sideview 2 nm ✑onoh✒✓ri✓e Silicon H H H H
  41. 41. 10 nm 1 nm Haiku Stripes
  42. 42. Hai✔u ✕tripe ✖o✗✘✙ ✚i✚i ✛ i ✜ e ✢ iew 5 7 5 7 5 ✣i
  43. 43. Haiku Stripe Model ✤ i ✥ e ✦ iew 5 7 5 7 5 H H H H H H Si
  44. 44. Haiku Stripe Model sideview 5 7 5 7 5 H H H H H H Si Field, CC-BY-SA skrewtape (Flickr)
  45. 45. Haiku Stripe Model sideview 5 7 5 7 5 H H H H H H Si Field, CC-BY-SA skrewtape (Flickr) Bulbs, CC-BY-SA, brewbooks (Flickr)
  46. 46. How can we be sure that it is a silicon only structure?
  47. 47. X-Ray Photospectroscopy Eγ X-ray e- Ekin Spectrometer Ekin Eγ Core levels Valence band Φ e- Binding energy (XPS)
  48. 48. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal
  49. 49. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi
  50. 50. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi Bi-exposed sample after H exposure
  51. 51. X-Ray Photospectroscopy Binding energy [eV] [Electroncounts/s] O C B O Si Si Si Si Si Clean Si monocrystal Bi Bi Bi Bi Bi-exposed sample before H exposure Bi Bi-exposed sample after H exposure
  52. 52. STM Simulations In collaboration with Prof. D. Bowler UCL & LCN Relaxed structure STM simulation Charges densities
  53. 53. 1 nm Filled States simulation experiment High current (200 pA) simulation experiment Low current (80 pA)
  54. 54. simulation experiment Cross Section 1.54 nm 70pm 5 pm Height Width simulation oset -10 pm experiment 1 nm
  55. 55. Empty States +2.5 V Simulations + 2.5 eV Data
  56. 56. Empty States +2.5 V Simulations + 2.5 eV Data 3 nm +2.0 V 1 nm + 1.0 eV
  57. 57. Charge Densities 3 nm Sideview
  58. 58. What else?
  59. 59. Air Resistant Exposed to air for 25 min 3 nm
  60. 60. Micrometer Long 200 nm 50 nm
  61. 61. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air
  62. 62. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air Delocalized electronic state Perfectly matching model
  63. 63. Self-assembled Stable to 400°C (in UHV) Micrometer long Properties Summary Tunable density Inert in air Delocalized electronic state Perfectly matching model Contacting Probing 1D physics &
  64. 64. What about Physics? Contacting Electrode Clamp Silicon 1 mm Mask deposition
  65. 65. 20 nm Markers & Contacts APL 100, 103103 (2012) Au markers Gold depositionExample
  66. 66. Optical measurement Doping Spectroscopy I(+1.5 V) What about Physics? 2 nm Outlook:
  67. 67. 1D Dan l n Bon s Rows ❆✧★ ◆ano (2013)
  68. 68. Hydrog✩nation 42✵✪✫ Synthesis
  69. 69. Assemb✬y Interests Molecular molds Atom assembly Annu. Rev. Phys. Chem. 60, 193 (2009) PRL 91, 136104 (2003) Gallium Phosphine Both examples were sequentially made
  70. 70. Haiku DB ✯ows H H π* π sideview Hydrogenated Si dimer Dangling Bond (DB)
  71. 71. 10 n H✰B Rehydrogenated
  72. 72. Central Dimer Model✳3DviewSideview H H H H Buckled Flat H H H H
  73. 73. H Binding Energy H atom on Si(001) 4.37 eV +0.16 +0.13 -0.10 -0.15 + - More stable Less stable EB/H[eV] sideview H H H H Buckled Flat H H H H -0.15 +0.13 -0.10 +0.16 From DFT calculations
  74. 74. Missing Hydrogen6% Si terraces % of dehydrogenated Si atoms
  75. 75. Missing Hydrogen6% Si terraces % of dehydrogenated Si atoms85% Haiku stripe
  76. 76. Alternating Flat Dimers + 1.8 V - 1.8 V
  77. 77. Alternating Flat Dimers + 1.8 V - 1.8 V Spin-polarized structure? Test at room temperature Outlook:
  78. 78. Properties Summary Micrometer long Highly reactive template Self-assembled Known structure
  79. 79. Properties Summary Micrometer long Highly reactive template Self-assembled Known structure Assembling 1D molecular or atomic chains
  80. 80. Con l s on
  81. 81. ✴✻mmary Self-assembly Lego bricks, CC-BY-SA dbesham (Flickr) Haiku stripes Haiku DB rows Bismuth nanolines
  82. 82. Summary Haiku stripes Haiku DB rows
  83. 83. FONDS NATIONAL SUISSE SCHWEIZERISCHE NATIONALFONDS FONDO NAZIONALE SVIZZERO SWISS NATIONAL SCIENCE FOUNDATION FN NFS ✼✾anks & ❏❛✿❀s ❁●❁❖we❂❃❄❣❅❊❂❍❁■öster ◗❲oup photo, ➞❬❭❪❫❴❵❥♦s
  84. 84. "Atomic hashi. A pair of Bismuth dimers, On Silicon core. Remove all Bismuth, Silicon in silicon. Atomic template." James H.G. Owen 5 7 5 7 5 H H H H H H Si

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