SYNTHESIS MECHANISM OF NANOWIRES

AND NANOTUBES

by

RAJASEKARAKUMAR
VADAPOO

UPR Physics Dept., Rio piedras Campus, San juan, PR-00931, USA.

More info: http://nanophysics.wordpress.com/

Differences between growth methods &
growth mechanism

Growth methods PVD, CVD, Solution techniques, …..

How one dimensional growth occurs

Growth mechanism Provide a kinetic & thermodynamic rationale

Be predictable & applicable to a wide

variety of systems
 General synthetic strategies for 1D growth

Dictation by the anisotropic

crystallographic structures of a solid.

The introduction of a liquid/ solid
interface to reduce the symmetry of the
seed.

direction through the use of a
template.

kinetic control provided by a
capping reagent.

self assembly of 0D nanostructures.

size reduction of a 1D
microstructure.
Fig.1. General strategies for 1D growth

Mat Law et al., Annu. Rev. Mater. Res. 2004, 34:83-122

 VLS ( Vapor- Liquid- Solid) Mechanism
-Self Catalytic VLS
Shown to produce high
VS ( Vapor- Solid) Mechanism quality materials

Solution-Phase selective Capping Mechanism

VLS

Pure & Doped Inorganic Materials

III-V Compounds II-VI Compounds Oxides, Carbides & Nitrides

( GaN, GaAs, GaP, InAs) ( ZnS, ZnSe, CdS, CdSe) (InSnO, ZnO, MgO, SiO2,
CdO, SiC, B4C, Si3N4 )
 VLS- mechanism

Key Steps

Establishment of
symmetry breaking Solid-
Liquid interface -important

Stoichiometry, Lattice
symmetry- less relevant

Fig.2. a) Schematic of VLS process

b)Gold- Ge binary phase diagram
Wu y, Yang P.,Am. Chem. Soc., 2001, 123:3165-66
 Advantages:

high purity

High uniformity in diameter

Usual dia.: 10 nm

length : > 1µm

Challenges:

Only for Eutectic compound

Contaminant of the Seed
metal.

Fig.3. a) Au nanoclusters in solid state at 500◦C

(b) alloying initiates at 800◦C, at this stage Au exists
mostly in solid state (c) liquid Au/Ge alloy;
(d) the nucleation of Ge nanocrystal on the alloy surface;
(e) Ge nanocrystal elongates with further Ge
condensation & (f) eventually forms a wire.

Wu y, Yang P.,Am. Chem. Soc., 2001, 123:3165-66

Fig. 4. (a) Field-effect scanning electron
microscope (FESEM) image of the GaN
nanowires grown on a gold-coated c-
plane sapphire substrate. Inset shows a
nanowire with its triangular cross section.
(b) TEM image of a GaN nanowire with a
gold metal alloy droplet on its tip. Insets
are electron diffraction patterns taken
along the [001] zone axis. The lower inset
is the same electron diffraction pattern
but purposely defocused to reveal the
wire growth direction.
(c) Lattice-resolved TEM image of the
nanowire.

Kuykendall T et al., Nano Lett., 2003, 1063-66

 Self- Catalytic VLS

Temp: > 8500C & Press: 10-7 torr.

GaN (s) → Ga (l) + 0.5 N (g) + 0.25 N2(g).

&
GaN (s) → GaN (g) or [GaN]x (g).

Challenges:

Precise control of nanowire length &
diameter- yet to demonstrate.

Versatility of this approach – yet to
demonstrate.
Fig. 5. A series of video frames grabbed from
observations of GaN decomposition at ~1050◦C,
showing the real-time GaN nanowire growth
process. The number on the bottom left corner of
each frame is the time (second:millisecond).
Stach EA et al., Nano Lett., 2003, 3: 867-69
 VLS- vapor phase methods

VLS- vapor phase Methods

Nanowire Growth
Fig.6. Simple vapor growth
Laser Ablation MOCVD MBE

Mobility of
Less High High
carriers

Integration to
the thin film Less High High
technology

Flexibility Normal Greatest Great

Mat Law et al., Annu. Rev. Mater. Res. 2004, 34:83-122

 VS - Mechanism
An anisotropic growth mechanism
(Binding of gas phase reactants along specific X’tal
Facets (TKP), min. surface energy (TP))

Frank’s screw dislocation mechanism

Thermodynamic &
(Specific defects- high sticking coefficient of gas
kinetic considerations- Phase species)
1D growth Different defect induced growth mechanism

Self catalytic VLS

Phase Rule
F+P= C+2
F No. of degrees of freedom
P No. of Phases
C No. of Chemical constituents

oxide assisted growth mechanism –success

structurally uniform

complex morphology

Lacks in compelling thermodynamic &
kinetic justification for 1D growth.
Fig. 7. phase diagram
Mat Law et al., Annu. Rev. Mater. Res. 2004, 34:83-122
 Growth in solution

poly vinyl pyrrolidone (PVP)- used

PVP- bind the {100} facets of silver

{111} facets to allow growth

controllable dia.: 30- 60 nm

length: ~50 µm

Fig.8. solution growth mechanism

Hydrolysis of Zn salt in the presence of amines

controllable dia.: 30-100 nm.

Length: 2-10 µm.

Fig. 9. ZnO nanowires using solution growth

Sun Y et al., Chem. Mater., 2002, 14:4736-45,
Greene LE et al., Angew. Chem. Int. Ed., 2003, 42:3031-34
 Hetrostructures Longitudinal

Si/ SiGe

coaxial

Fig. 11. Si/ SiGe hetrostructure using PLD

GaN/ AlGaN

Wu Y et al., Nano Lett., 2002, 2: 83-86

Gudiksen MS et al., nature, 2002, 415:617-20
Bjoerk MT et al., Nano lett., 2002,2:87-89
 Conclusion

Synthetic capabilities continue to expand quickly

Several outstanding scientific challenges need to be addressed

integration & interfacing problems

precise control over- size uniformity, dimensionality, growth

direction, dopant distribution within the semiconductor
nanostructures

accurate appropriate theoretical simulations

 Back- Ups

Substrate Source Materials

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