Epitaxial growth and study of 2D

Se-based ultrathin films: Bi2Se3,

MoSe2, HfSe2 , ZrSe2
Aretouli E. Kleopatra
20/2/15
NCSR DEMOKRITOS, Athens, Greece

Outline
Topological insulators: Bi2Se3
MBE growth and structural characterization
Semiconducting Transition metal dichalcogenides
(TMDs)
MoSe2
HfSe2
ZrSe2
Conclusions/ Future work

3D Topological Insulators
Bi2Se3 , Bi2Te3, Bi1-xSbx

Spin locked to orbital momentum

Gapless metallic surface states

Spin polarized (helical) Dirac cones

relativistic movement of e- :

light-like particles

insulating bulk

Topologically protected
spin
-k

k
e-

-k

Non-magnetic
impurity

-k

Backscattering is suppressed
Novel switching mechanisms/functionalities

Y. Xia et al., Nat. Phys. 5, 398 (2009)

Ultra high vacuum champers for growth and structural

characterization

XPS

RHEED
STM

MBE

ARPES

HRTEM and XPS

Substrates : 200 nm AlN(0001) /200 mm Si (111)

3QL epitaxial Bi2Se3

Thick ~ 20 Quintuple Layers (QL)

Bi2Se3/AlN
No reaction sharp
crystalline interfaces
1 QL ~ 1 nm

1 QL

[11-20]
*P. Tsipas et al., ACS Nano, 8 (7), 6614 (2014)

High epitaxial quality and clean crystalline interfaces

Gapless surface states in ultrathin Bi2Se3

In-situ ARPES

Ultrathin films: Hybridization-gap opening

Thick films (>6QL exp.): Non-interacting

3 QL Bi2Se3/AlN(0001)

2nd derivative
EF

Gapless
surface
states

surface
states

EB (eV)

EB (eV)

CB

5 QL Bi2Se3/AlN(0001)

2nd derivative
Gapless
EF

0.47 eV

VB
k//,y (-1)

k //,y (-1)

k //,y (-1)

k //,y (-1)

3QL: Thinnest Bi2Se3 with gapless surface states (Dirac cone) ever reported
experimentally !
Reduce surface to volume ratio - applications in nanoelectronics

Heterostructures with Chemically compatible semiconductors

Two Layer MoSe2 on Bi2Se3Template
RHEED

2ML MoSe2 at 300 oC

2ML MoSe2/5QL Bi2Se3

5QL Bi2Se3 at 300 oC

AlN [11-20] azimuth

3QL Bi2Se3/2ML MoSe2/3QL Bi2Se3

aAlN=3.11
aBi2Se3=4.14
mismatch of~ 33%

5 QL

aBi2Se3=4.14
aMoSe2=3.299
mismatch of ~20%

Perfect alignment of the 2 hexagonal lattices

[11-20] MoSe2 //[11-20] Bi2Se3 // [11-20] AlN
No rotated domains-single crystal

Semiconducting 2D Transition Metals Dichalcogenides (TMDs)

Layered TMDs crystals of the composition MX2 :
M: transition metal (VIB: Mo, W and IVB: Zr,Hf )
X: Chalcogen species (S, Se, Te)
Honeycomb like structures

superior properties to those of graphene ???

2H structure

1T structure

Se

Se

Mo

6.5

y
z

Hf
y

Indirect to direct band gap

crossover when thickness reduces to
a single layer
MoSe2 : E. Xenogiannopoulou et al. submitted 2014

Indirect band gap

very close to Si
HfSe2 : K.E. Aretouli et al. submitted 2015

anisotropic mechanical optical and electrical properties

Sizable band gap in the visible and NIR region of the solar spectrum
Applications in Optoelectronic devices(energy conversion systems)
and Field Effect Transistors/ low power logic devices

RHEED, TEM, STM of 3ML MoSe2/AlN(0001)

Two step growth process
d

AlN

AlN
AlN

vdW gap

MoSe2

MoSe2
MoSe
MoSe
2 2
350C

Bi2Se3
300C

350C
350C
350C

f
MoSe
MoSe2 2

MoSe2

MoSe2

690C

300C

690C
690C

STM image: honeycomb structure

Line 1

3.3

Se

Se

Se

1
Line 2

Mo

Se
Mo

estimated distance of 3.3 between Se-Se atoms ~ aMoSe2=3.299

Valence Band Imaging

He I

1st Brillouin
zone
MoSe2
L

(a)

6ML
/
(c)

(b)

4
Binding Energy (eV)

EF

3 ML
/
/

1ML MoSe2

H
K

KMoSe2 =1.274

-1

He I

He II

2
0
-2
-4

EF

(e)

(d)

KM

(f)

Shift of VB at -point

to higher binding energy

Indirect to direct band
gap transition in the
1ML limit

He II
k// ,y( )

E. Xenogiannopoulou et al. submitted 2014

-1

k//,y ( )
-1

k//,y (-1)

RT measurements

Raman and PL characterization of MoSe2 films at

ML-limit on AlN(0001)
-1

295 K

log(Intensity) (a.u.)

Intensity
Intensity (a.u.)
(a.u.)

Si 521cm-1

=532 nm

2 mW

MoSe2
2

-1
-1

A1g 240.8 cm
1g

Si peak

PL
PL Intensity
Intensity (a.u)
(a.u)

200

400

=532 nm
2
I=2mW/m2

1.2

600

800 1000
-1

Raman Shift (cm-1)

A B
190 meV

B (1.75eV)

1.6

Energy (eV)

1.8

High
E12g

2.0

Si

Low

B12g
Breathing
mode

250

300

350

-1

400

Raman shift (cm)

1200

1.4

A1g

200

295 K

A (1.55eV)

0.3cm
0.5cm
0.7cm
0.9cm
1.1cm
1.3cm

Active modes of MoSe2:

A1g at 240.8 cm-1
E2g at 288.5 cm-1
B2g at 352 cm-1 in few layer
material

The direct band gap in single layers results in

intense room temperature photoluminescence (PL)
Applications from optoelectronics to energy
conversion

HfSe2 and MoSe2 / HfSe2 films on AlN(0001)

6ML HfSe2

HfSe2 deposition at 570 oC

(a) M
Annealing at 810 oC

Absence of strain
aHfSe2=3.78
v.d. Waals heteroepitaxy

/L

Binding Energy EB (eV)

XPS

kx (-1)

(b)

DFT

calculations

Energy (eV)

AlN
1ML HfSe2
6ML HfSe2
3ML MoSe2

mismatch
mismatch of
of ~15%
~15%

mismatch
mismatch of
of ~6%
~6%

[11-20] azimuth

K/H

1
Ef

0
-1
-2
-3
-4
-5

Conclusions
Thinnest Bi2Se3 (3QL) with gapless surface states
(Dirac cone) ever reported experimentally
High structural quality MoSe 2 and HfSe2 on AlN/Si
substrates
MoSe2/Bi2Se3 and MoSe2/HfSe2 multilayers can be
produced
Future work
Exploring the semiconductors HfSe 2, ZrSe2
Electrical characterization of Bi2Se3, MoSe2 HfSe2 ,
ZrSe2 and their heterostructures
Magnetoresistance measurements/ Hall effect
measurements