MatSci 193/203:

Atomic Arrangements in Solids

Macroscopic properties from microscopic

symmetry

Evan Reed
November 28, 2016

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 For additional reference
• Primary reference: Nye handouts on
Coursework

• Kelly and Knowles chapters 5 and 6

(electronically available through SU library)

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Point group
symmetry impacts a
wide range of
material properties

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 Neuman’s Principle
• Neuman’s Principle: The symmetry
elements of any physical property of a crystal
must include the symmetry elements of the
point group of the crystal.

• This principle can be used to determine the

form of tensors that describe physical
properties.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 A novel
application of a
LiTaO3
pyroelectric xtal

LiTaO3 is trigonal at ambient

conditions. Space group R3c.
Point group 3m.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
Pyroelectric-driven fusion

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
Pyroelectric
-driven
fusion

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
Symmetry properties of rank 2 tensors
What could cause anisotropic expansion of
lithiated single crystal Si (Fd3m) anodes?
Stress tensor is rank 2
Integrating PIEZOELECTRICITY
Piezoelectric
Dynamic Control
Applications
in Nanodevices

Piezoelectric Effect Converse Piezoelectric Effect

Pi=eijkejk eij=dijkEk

++++++++

Polarization Electric
Field

- - - - - - - -

Piezoelectric materials must exhibit:

1. An electronic bandgap
2. A lack of centrosymmetry

Inversion symmetry of a crystal => dijk = (-1)3

dijk = -dijk
So dijk=0 for crystals with inversion symmetry!
 PIEZOELECTRIC
Integrating
Piezoelectric CONDITION:
Dynamic Control
Applications NON-
in Nanodevices
CENTROSYMMETRY

Centrosymmetric
Non-polar.

ΔP = 0.
Non-centrosymmetric
Polar!

ΔP allowed.
 CANPiezoelectric
IntegratingANY OF THESE
Dynamic Control CRYSTALS
Applications BE
in Nanodevices
PIEZOELECTRIC?

These are the 14 Bravais

lattices with one atom per
lattice point.
 SOME
Integrating PIEZOELECTRIC
Piezoelectric
Dynamic Control in MATERIALS
Applications
Nanodevices

Wurtzite structure: Perovskites can be piezoelectric

ZnO, GaN, AlN, etc. and ferroelectric: BaTiO3,
PbZrxTi1-xO3, etc.
Symmetry properties of rank 3 tensors
(piezoelectric, nonlinear susceptibility)
 TMD MONOLAYERS HAVE POTENTIAL
FOR PIEZOELECTRICITY
Transition Metal Dichalcogenides:
MoS2, MoSe2. MoTe2, WS2, WSe2

Trigonal prismatic
structure:
Semiconducting (Egap ~ 1-2 eV)
Not centrosymmetric
3m point group leads to non-zero
d11 and e11 coefficients
WEOur
DISCOVER THAT A VARIETY
HPC-enabled OF TMDS
approach HAVE
enables
SIGNIFICANT PIEZOELECTRIC
identification EFFECTS
of promising materials

Piezo-coefficients of
trigonal prismatic TMD K.-A. Duerloo, M. T. Ong, E. J. Reed., J.
structures are comparable Phys. Chem. Lett. 3, 2871 (2012).
to bulk wurtzite structures
Bulk: p63/mmc (6/mmm) Monolayer: p3m (3m)

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
Bilayer MoS2 exhibits an inversion
center between the layers.

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
 PIEZOELECTRICITY IN 2D MATERIALS HAS
RECENTLY BEEN OBSERVED
“Observation of Piezoelectricity in
monolayer MoS2,” Zhu, Wang, Xiao,
Liu, Xiong, Wong, Ye, Yin, Zhang,
Nature Nanotechnology (2014).

“Piezoelectricity of single atomic layer

MoS2…” Wu, Wang, Hone, Wang et al.,
Nature (2014).

Piezoelectricity in
C3N4 few layers:
Zelisko, et al, Nature
Communications
(2014).
 KDP crystal for
frequency doubling

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University
MatSci 193/203: Atomic Arrangements in Solids
Evan Reed
Stanford University
Symmetry properties of rank 4 tensors
(elastic compliance)
Which of these are space groups and to
which crystal system (symmetry) do they
belong?
P63/mmc
C2/c
I222
R2d2
I41/acd
R3c
P6422
F23
C3po
 MatSci 193/203 course objectives

• What: Common crystalline structures for

research-relevant materials
• Why: Why these structures are what they are;
The nature of chemical interactions in materials
• Implications: Macroscopic manifestations of
microscopic (atomic) structure (mechanical
properties, etc.)

MatSci 193/203: Atomic Arrangements in Solids

Evan Reed
Stanford University