CHEM 391 2017

Materials Chemistry
Lecture 5: One Dimensional Nanomaterials
 Other core/shell nanoparticles
Case 1: Au/SiO2 core/shell nanoparticles

Motivation: tuning optical properties of Au nanoparticles.

TEM images of Au@SiO2 particles produced during the growth of the silica
shell around 15 nm Au particles. The shell thicknesses are (a)10 nm, (b) 23
nm, (c) 58 nm, and (d) 83 nm.
Liz-Marzan LM, Giersig M, Mulvaney P, Langmuir, 1996, 12, 4329.
 Case 2: FeCo/graphite core/shell nanoparticles
Motivation:
- FeCo has superior magnetic properties, but it has yet to be explored owing to the problems of easy
oxidation and potential toxicity.
- There is potential of using these nanocrystals for integrated diagnosis and therapeutic
(photothermalablation) applications.

Key procedure:
- Loading Fe and Co species onto high surface-area silica powder by impregnation in a methanol solution
of mixed Fe and Co salts.
- Metal-loaded silica was heated to 800 oC under H2 and then subjected it to methane chemical
vapour deposition (CVD) for carbon deposition on FeCo nano-alloy formed on silica.
- SiO2 was etched away by HF.

surface modifications

Dai HJ et al., Nature Materials, 5, 971-976 (2006)

structural characterizations
History: silicon whiskers (1964)

Wagner, R. S.; Ellis W. C. Applied Physics Letters, 4, 89-90 (1964).

History: silicon whiskers (1964)

Wagner, R. S.; Ellis W. C. Transactions of the metallurgical society of AIME, 233, 1053(1965).
 Si/Au phase diagram

Temperature dependence of the kinetic

Wagner, R.S. Whisker Technology, ed. by AP Levitt coefficients and determination of the activation
(Wiley, New York 1970) p. 47. energy for Si whisker growth.

Givargizov, E. I. Fundamental aspects of VLS growth.

Journal of Crystal Growth, 31. 20-30 (1975).
History: silicon whiskers (early 1990s)

Haraguchi, K.; Hiruma, K.; Yazawa, M.; Katsuyamaz, T.

Hitachi, Limited, Central Research Laboratory, Japan.
Overview of Synthetic Methods
 How to promote one dimensional (1-D) growth?
(a) Growth of an intrinsically anisotropic crystallographic structure,

(b) The use of various templates with one dimensional morphologies to direct the
formation of one-dimensional nanostructures,

(c) The introduction of a liquid/solid interface to reduce the symmetry of a seed,

(d) Use of an appropriate capping reagent to control kinetically the growth rates of
various facets of a seed,

(e) The self-assembly of 0D nanostructures.

 Vapor-phase approaches
1. Vapor-liquid-solid growth
In situ TEM images recorded during the process of Ge nanowire growth

Yang P.D. et. al. J. Am. Chem. Soc. 123, 3165–3166 (2001).

Key steps:
(1) Generation of gaseous reactants.

(2) Dissolution of gaseous reactants into nano-sized liquid droplets of a catalyst metal.

(3) Nucleation and growth of single-crystalline rods and then wires. Each liquid droplet serves as a
virtual template to strictly limit the lateral growth of an individual wire.
 Vapor-phase approaches
2. Vapor-solid growth
(a) An anisotropic growth mechanism

Preferential reactivity and binding of gas phase reactants along specific crystal facets
(thermodynamic and kinetic parameters) and also the desire for a system to minimize surface
energies (thermodynamic parameter).

(b) A defect-induced growth mechanism

Specific defects (for example screw dislocations) are known to have larger sticking coefficients for
gas phase species, thus allowing enhanced reactivity and deposition of gas phase reactants at these
defects.

(c) Oxide-assisted growth mechanism

Lee, S. T. et. al. Advanced Materials, 15, 635–640 (2003).

However, many of these proposed vapor-solid growth mechanisms lack compelling

thermodynamic and kinetic justification of one-dimensional growth.
Silicon Nanowires

• Vapor phase synthesis

• Solution phase synthesis

 Vapor phase synthesis
Breakthrough work --- laser-assisted catalytic growth of silicon nanowires

Schematic of the nanowire growth apparatus

(1) output of pulsed laser

(2) lens
(3) target (Si0.9Fe0.1)
(4) tube furnace
(5) cold finger
(6) pump system

nanowire structural characterization

Morales, A. M.; Lieber, C. M. Science, 279, 208-211 (1998).
 Proposed silicon nanowire growth model

(A) Laser ablation with photons of energy hn of the Si1-xFex target creates a dense, hot vapor of Si
and Fe species.

(B) The hot vapor condenses into small clusters as the Si and Fe species cool through collisions with
the buffer gas. The Si-Fe nanocluster is maintained in a liquid (Liq) state at furnace
temperature.

(C) Nanowire growth begins after the liquid becomes supersaturated in Si and continues as long as
the Si-Fe nanoclusters remain in a liquid state and Si reactant is available.

(D) Growth terminates when the nanowire passes out of the hot reaction zone (in the carrier gas
flow) onto the cold finger and the Si-Fe nanoclusters solidify.

Morales, A. M.; Lieber, C. M. Science, 279, 208-211 (1998).

 Diameter controlled growth

Schematic illustrating size-controlled synthesis

SiH4, NW growth

AFM image of 10 nm Au nanoclusters

SEM and TEM images of Si NWs

Cui, Y. et. al. Applied physics letters, 78, 2214-2216 (2001).

 Diameter controlled growth

Histograms of SiNW diameters grown from (a) 5, (b)10,

(c)20, and (d)30 nm diameter Au nanoclusters.

TEM images of SiNW of (a) 6.7 nm, (b) 10.7 nm, and
(c) 20.6 nm diameter NWs grown from 5, 10, and 20
Cui, Y. et. al. Applied physics letters, 78, 2214-2216 (2001). nm catalysts, respectively.
 Molecular scale silicon nanowires

20 nm

5 nm

Why molecular wire possible?

(1) Small Au catalyst, 2-5 nm.
(2) H2 passivation gives clean surface.
(3) Exposed (100) and (111) solid/vacuum interfaces have
lowest free energy.
(4) liquid/solid (111) interface remains the lowest energy
interface.
Wu, Y. et. al. Nano Letters, 4, 433-436 (2004).
 Si NW growth direction vs. diameter

Number density versus diameter for different growth

directions. (Inset) relative proportion of the different
growth directions.

Histograms of the growth directions for SiNWs with diameters

from (a) 3 to 10 nm, (b) 10 to 20 nm, and (c) 20 to 30 nm.
Gosele U. et. al. Nano Letters, 5, 931-935 (2005).
Wu, Y. et. al. Nano Letters, 4, 433-436 (2004).
 Si NW growth direction vs. diameter

Contributions that are growth-direction-dependent:

(1) liquid-solid interfacial tension (σls)

F: free energy
(2) surface tension Si (σs)
L: circumference
edge tension,
geometry parameter:
<111>:
f: free energy per circumference
<110>:

rc ~ 10 nm

Gösele U. et. al. Nano Letters, 5, 931-935 (2005).

 Doping of silicon nanowires

Introduce Dopants

• Conductivity of silicon can be varied several orders of magnitude by

introducing impurity atoms, called dopants.

• acceptors: accept electrons to leave holes in silicon, lead to p-type silicon (e.g.
Boron)

• donors: provide electrons to silicon, lead to n-type silicon (e.g. Arsenic,

phosphorus)

Doping Methods in Microelectronics Manufacturing

• Deposition through diffusion

– evaporating dopant material into the silicon surface
– thermal cycle: impurities diffuse deeper into material

• Ion Implantation
– silicon surface subjected to highly energized donor or acceptor atoms
– Dopant atoms impinge silicon surface, and drive below it to form regions of varying concentrations

Doping in silicon nanowires is more challenging!

 Doping of silicon nanowires

Aproach-1, laser-assisted catalytic growth and doping

Key synthesis:

Boron doping: incorporating B2H6 in the reactant flow

Phosphorus doping: using a Au-P target (99.5:0.5 wt %, Alfa Aesar) and additional red
phosphorus (99%, Alfa Aesar) at the reactant gas inlet.

Key features:
+ First example of synthesis and electrical characterization of silicon nanowires with p- and n-
type doping, suggesting their important applications in nanoelectronics.

- The doping method is less controllable.

- The electronic properties (e.g. mobilities) of doped Si nanowires need to be further improved.

Cui, Y. et. al. J. Phys. Chem. B, 104, 5213-5216 (2000).

 Doping of silicon nanowires
Aproach-2, homogeneous chemical vapor deposition
Key synthesis:

Boron doping: incorporating B2H6 in SiH4 gas flow, e.g. 2 sccm of SiH4, 2.5 sccm of B2H6 (100
ppm), 60 sccm of H2 (carrier gas), 40 torr, 450 oC, 10-30 min.

Phosphorus doping: incorporating PH3 in SiH4 gas flow, e.g. 2 sccm of SiH4, 0.5 sccm of PH3
(1000 ppm), 60 sccm of H2 (carrier gas), 40 torr, 460 oC, 10-30 min.

Key features:

+ Most reliable and easy method for silicon nanowire

doping.
+ the doping ratio can be readily controlled by
varying the feeding ratio of SiH4 and gaseous dopant
precursors.
- The decomposition of SiH4 can be promoted by
SiH4, while inhibited by PH3. Thus there could be
overcoating and tapering issue associated with p-
type silicon nanowire synthesis. The synthesis
under H2 atmosphere and lower temperature can
help solve such issue.

Zheng, G. F. et. al. Advanced Materials, 16, 1890-1893 (2004).

 Doping of silicon nanowires
Aproach-3, molecular monolayer doping
Motivation: controlled, nanoscale doping of semiconductor materials

Boron monolayer doping (p-doping) of Si. a), Secondary-ion mass spectrometry (SIMS) profile for 5 s annealing
at 950 and 1,000 oC. b), Sheet resistance versus time at different RTA temperatures.

Javey, A. Nature Materials, 7, 62-67 (2008).

 Ab initio study of doping in silicon nanowires
Key results:

(1) B and P dopants are found to migrate to the edge of the wire and that the formation energy for codoping is
smaller than that for the single doped cases.

(2) P dopants are found to be more easily trapped, and thus become electronically inactive, than B dopants.

The formation energy as function of the position (labeled according

cross section model of the 1.6 nm to schema shown on the left) for the 1.6 nm wire for (a) B doping, (b)
Si nanowire P doping, and (c) B,P codoping.

Peelaers, H. et. al. Nano Letters, 6, 2781-2784 (2006).

 Reference List

Wagner, R. S.; Ellis, W. C. Vapor-liquid-solid mechanism of single crystal growth. Applied Physics Letters, 4, 89-90 (1964).
Givargizov, E. I. Fundamental aspects of VLS growth. Journal of Crystal Growth, 31. 20-30 (1975).

Wu, Y.; Yang, P. Direct observation of vapor-liquid-solid nanowire growth. J. Am. Chem. Soc. 123, 3165–3166 (2001).

Zhang, R. Q.; Lifshitz, Y.; Lee, S. T. Oxide-assisted growth of semiconducting nanowires. Advanced Materials, 15, 635–640 (2003).

Morales, A. M.; Lieber, C. M. A Laser Ablation Method for the Synthesis of Crystalline Semiconductor Nanowires, Science, 279,
208-211 (1998).

Cui, Y.; Lauhon, L. J.; Gudiksen, M. S.; Wang J. F.; Lieber C. M. Diameter-controlled synthesis of single-crystal silicon
nanowires, Applied physics letters, 78, 2214-2216 (2001).

Wu, Y.; Cui, Y.; Huynh, L,; Barrelet, C. J.; Bell, D. C.; Lieber, C. M. Controlled Growth and Structures of Molecular-Scale Silicon
Nanowires. Nano Letters, 4, 433-436 (2004).

Schmidt, V.; Senz, S.; Gösele U. Diameter-Dependent Growth Direction of Epitaxial Silicon Nanowires, Nano Letters, 5, 931-935
(2005).