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Synthesis and characterization of
individual ZnO nanowires


                             M. Duchamp
“Nano” applications
MEMs device to measure ZnO                                    Piezoelectronic
 nanowires Young’s modulus
                                                        Field Effect Transistor (FET)




                                                     Xudong Wang et al. Nano Lett., Vol. 6, No. 12, 2006
R. Agrawal et al. Nano Lett., Vol. 8, No. 11, 2008
“Nano” applications
 • Direct-Current nanogenerator driven by
   ultrasonic waves




Xudong Wang, et al. Science 316, 102 (2007)
Top-Down approach

• Today technology: last Intel node




                  Improved transistor density by 2

• Complex and expensive processes
• Need of new materials
ZnO attractive properties



• Hexagonal wurtzite structure

• ZnO can be used as UV or blue emitting
  materials
• Transparent in visible spectrum

• Wide band gap: 3.36 eV at room temperature
• Young’s modulus: 140 GPa
Chemical Vapor Deposition Synthesis

• Using Vapor-Liquid-Solid (VLS) growth mode
                             Dissolution
                             Diffusion
                             Super-saturation
                             Oxidation




900°C for 20 minutes
Argon and Oxygen gas
Diameter control




 Minimum achievable diameter: 40nm
Gold colloid catalysts

                                              Density of
Chemical
                                               colloid
functionalization
                                                  ∞
silicon substrate
                                             Immersion
                                                time
Zinc precursor



 How did we chose the                                 Influence of zinc/oxygen
 reaction temperature?                                ratio in the gas phase
        ZnO (s)




                                         Zn (g)




Lan Hong et al. Scandinavian Journal of Metallurgy, 171–176, 2006
Rajoute diffraction pattern
                Crystallographic orientation
                             Sapphire (001)            SrTiO3 (110)




   C-axis




                                                     Lattice mismatches :
Silicon (100)             Lattice mismatch : 18.8%   1% and 9%
Dielectrophoresis of ZnO nanowires

                                               Parameters studied:
                                               • Dispersion
                                               • Solvents
   Repartion [%]




                                               • Substrates
                                               • Applied voltages


                   Number of attracted Nws


   Number of ZnO nanowires between electrodes can
    be controlled by the applied voltage

M. Duchamp, Kyumin Lee et al. in preparation
Electrical measurements: contact effects
Lithography
                                Contact oxidation
lift-off processes




                                Nitrogen doped Cr is
                                used as metal
                                Cannot be oxidized



                                    Allen et al. Appl. Phys. Lett. 94 (2009)
Energy level in semiconductors

 • Schottky diode




• Electron affinity ZnO: 4.5eV
• Work function Cr: 4.5eV
Transport measurements




                   2 eV
Optical measurements
                                                                     Catholuminescence by Scanning
                   Photoluminescence                                   Tunneling Microscopy
                                                                              3.3eV
                                               ZnO1
                   1.0                         ZnO3
                                               ZnO4
                                               ZnO2
Intensity (a.u.)




                   0.8


                                                                                  2.1eV
                   0.6


                   0.4


                                                                            3.3eV 2.4eV
                   0.2


                   0.0
                      200    400   600   800    1000   1200   1400

                                   Wavelength (nm)
                            Excitation: 330-360 nm
                            Optical gap: 2.3eV
Mechanical properties




                TEM compatible substrate




                                  32nm
                                  120GPa
Young’s modulus of ZnO nanowire

                                          Catalyst free growth
                                          by CVD in oxygen rich
                                          atmosphere




                                                          32nm




                                                          40nm
Young ‘s modulus higher
 than bulk value
C. Q. Chen et al. PRL 96, 075505 (2006)
Conclusions


• Control of the synthesis:
  – Diameter, Shape, Length
• Semi-conducting properties of ZnO grown by
  VLS method have been extracted fom a single
  nanowire
• Young modulus enhanced for stoichiometric
  nanostructures

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Synthesis And Characterization Of Individual ZnO Nanowires

  • 1. Synthesis and characterization of individual ZnO nanowires M. Duchamp
  • 2. “Nano” applications MEMs device to measure ZnO Piezoelectronic nanowires Young’s modulus Field Effect Transistor (FET) Xudong Wang et al. Nano Lett., Vol. 6, No. 12, 2006 R. Agrawal et al. Nano Lett., Vol. 8, No. 11, 2008
  • 3. “Nano” applications • Direct-Current nanogenerator driven by ultrasonic waves Xudong Wang, et al. Science 316, 102 (2007)
  • 4. Top-Down approach • Today technology: last Intel node Improved transistor density by 2 • Complex and expensive processes • Need of new materials
  • 5. ZnO attractive properties • Hexagonal wurtzite structure • ZnO can be used as UV or blue emitting materials • Transparent in visible spectrum • Wide band gap: 3.36 eV at room temperature • Young’s modulus: 140 GPa
  • 6. Chemical Vapor Deposition Synthesis • Using Vapor-Liquid-Solid (VLS) growth mode Dissolution Diffusion Super-saturation Oxidation 900°C for 20 minutes Argon and Oxygen gas
  • 7. Diameter control  Minimum achievable diameter: 40nm
  • 8. Gold colloid catalysts Density of Chemical colloid functionalization ∞ silicon substrate Immersion time
  • 9. Zinc precursor How did we chose the Influence of zinc/oxygen reaction temperature? ratio in the gas phase ZnO (s) Zn (g) Lan Hong et al. Scandinavian Journal of Metallurgy, 171–176, 2006
  • 10. Rajoute diffraction pattern Crystallographic orientation Sapphire (001) SrTiO3 (110) C-axis Lattice mismatches : Silicon (100) Lattice mismatch : 18.8% 1% and 9%
  • 11. Dielectrophoresis of ZnO nanowires Parameters studied: • Dispersion • Solvents Repartion [%] • Substrates • Applied voltages Number of attracted Nws  Number of ZnO nanowires between electrodes can be controlled by the applied voltage M. Duchamp, Kyumin Lee et al. in preparation
  • 12. Electrical measurements: contact effects Lithography Contact oxidation lift-off processes  Nitrogen doped Cr is used as metal  Cannot be oxidized Allen et al. Appl. Phys. Lett. 94 (2009)
  • 13. Energy level in semiconductors • Schottky diode • Electron affinity ZnO: 4.5eV • Work function Cr: 4.5eV
  • 15. Optical measurements Catholuminescence by Scanning Photoluminescence Tunneling Microscopy 3.3eV ZnO1 1.0 ZnO3 ZnO4 ZnO2 Intensity (a.u.) 0.8 2.1eV 0.6 0.4 3.3eV 2.4eV 0.2 0.0 200 400 600 800 1000 1200 1400 Wavelength (nm) Excitation: 330-360 nm Optical gap: 2.3eV
  • 16. Mechanical properties TEM compatible substrate 32nm 120GPa
  • 17. Young’s modulus of ZnO nanowire Catalyst free growth by CVD in oxygen rich atmosphere 32nm 40nm Young ‘s modulus higher than bulk value C. Q. Chen et al. PRL 96, 075505 (2006)
  • 18. Conclusions • Control of the synthesis: – Diameter, Shape, Length • Semi-conducting properties of ZnO grown by VLS method have been extracted fom a single nanowire • Young modulus enhanced for stoichiometric nanostructures