CHEM 391 2017

Materials Chemistry II

Lecture 6: Doping, 2D materials

 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
L: circumference
(2) surface tension Si (σs) : 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 to

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

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

Introduction to Graphene
Graphene – Mother of all graphitic forms

Geim A. K. Novoselov K. S. Nature Materials, 6, 183-191 (2006).

 Isolating Graphene
In 2004, Andre Geim, Kostya Novoselov and co-workers at the University of Manchester in the UK
produced something that was long considered impossible: a sheet of crystalline carbon just one atom thick,
known as graphene, by delicately cleaving a sample of graphite with sticky tape. They were also able to
visualize the new crystal using a simple optical microscope.

https://www.youtube.com/watch?v=rphiCdR68TE
Just months after the initial discovery, Geim’s group improved its method for producing graphene. Rather
than ripping sheets of carbon from graphite with adhesive tape, the team produced higher-quality graphene
by gently pushing small graphite crystals along a hard surface – using a technique akin to drawing with a
pencil.

Soon after, a group headed by Philip Kim at Columbia University in the US confirmed the existence of
graphene using the same drawing technique.

Walt de Heer and Claire Berger at Georgia Tech developed an epitaxial growth process that may be suitable
for mass-producing graphene for industrial applications.
Physics world, Novemeber, 1-5 (2006).
First graphene device

Novoselov K. S.; Geim A. K. et al. Science, 306, 666–669 (2004).

 Graphene Nanoribbons (GNRs)
• Graphene nanoribbons essentially single layers of graphene that are cut in a
particular pattern to give it certain electrical properties.

• Depending on how the un-bonded edges are configured, they can either be in a
Zigzag or Armchair configuration.

• Zigzag GNRs are always metallic while armchairs can either be metallic or
semiconducting, depending on their width, with the energy gap scaling with the
inverse of the GNR width.
 Chemically derived graphene nanoribbons
Motivation:

Lithographic patterning of graphene sheets has fabricated GNRs down to widths of ~20 nm, but there are difficulties in
obtaining smooth edges (for example, with roughness < ~5 nm) and reaching true nanometer-scale ribbon width.

Key synthesis

• Exfoliation of commercial expandable graphite

by brief (60 s) heating to 1000°C in forming gas
(3% hydrogen in argon).

• The resulting exfoliated graphite was

dispersed in a 1,2-dichloroethane (DCE) solution
of poly(m-phenylenevinylene-co-2,5-dioctoxy-p-
phenylenevinylene) (PmPV) by sonication for 30
min to form a homogeneous suspension.

• Centrifugation then removed large pieces of

materials from the supernatant.

Dai H. J. et al. Science, 319, 1229-1232 (2008).

Chemically derived graphene nanoribbons

Tour J. M. et al. Nature, 458, 872-876 (2009).

 Other 2D Materials
Transition metal dichalcogenides (TMDCs)

K. S. Novoselov et al, Science, 353, aac9439 (2016).

Heterostructures of 2D Materials

K. S. Novoselov et al, Science, 353, aac9439 (2016).

Heterostructures of 2D Materials (stacked)

K. S. Novoselov et al, Science, 353, aac9439 (2016).

Heterostructures of 2D Materials (in plane)

K. S. Novoselov et al, Science, 353, aac9439 (2016).

2D Materials for Catalysis

Dehui Deng et al, Nature Nanotechnology, 11, 218 (2016).

2D Materials for Catalysis

Dehui Deng et al, Nature Nanotechnology, 11, 218 (2016).

2D Materials for Catalysis

Dehui Deng et al, Nature Nanotechnology, 11, 218 (2016).