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Photoluminescence from a few layered WS2

flakes prepared via top-down approach

Shivani Sharma, Shubham Bhagat, Naveen, Virpal,


Sanjeev Kumar and Sandeep Sharma

Department of Physics, Guru Nanak Dev University,


Amritsar, Punjab
Outline of Talk
1. Beyond Graphene? Why Transition Metal Di-
Chalcogenides (TMDCs) ?
-Band structure comparison

2. Experimental
- Sample preparation

- Structural characterization:
- XRD from bulk crystalline powder
- Raman active modes in WS2
- TEM Images on sample

- Optical measurements
- UV-Vis spectroscopy
- Photoluminescence from WS2

3. Summary 2
Band structure Graphene vs. TMDCs
Graphene TMDCs, WS2
Bulk Monolayer
Conduction band
electrons are free
to roam

No bandgap

E
Valence band
electrons are
bound to atoms
k
Pristine Graphene has linear relationship betn Source: Phys. Rev. B 83, 245213 (2011)
energy E and wave vector k
1. An indirect bandgap (Bulk) 1.3 eV at Γ point.
Absence of bandgap
1. make it unsuitable for logic device 2. In monolayer direct bandgap 2.05 eV at K-point
applications
2. Bandgap in Graphene can be introduced by 3. Suitable for Logic devices, Optoelectronics &
external E-field, doping or functionalization Photovoltaic devices
Beyond graphene ??
Transition Metal Dichalcogenides, new 2D-materials
Graphene TMDCs
1. Mobility is ≈ 105 cm2 V−1 s −1 1. Mobility is >60 cm2 V−1 s −1

2. Absence of bandgap make it unsuitable for 2.Presence of bandgap (upto 6 eV, conducting to
logic device applications insulating), Suitable for Logic devices, Optoelectro
& Photovoltaic devices.
3. Ion/Ioff ratio is low (≈104), due to large off state
leakage in devices 3. Ion/Ioff ratio is large (≈108), off state leakage is low

4. Bandgap in Graphene can be introduced by 4. Luminescence quantum efficiency 104X bulk


external E-field, doping or functionalization

Applications of (TMDCs) 2D nanomaterials


Nano-electronics (logic and lighting devices) Sensors (large surface area/volume ratio)

Spintronics (larger spin-orbit coupling) Hydrogen storage

Dielectrics Lubricant additives


Visible spectrum and bandgap in WS2

In visible region of spectrum the photon energy range from 1.6 eV to 3.1 eV

Bulk WS2 Eg ≈ 1.3 eV, near IR Region

Monolayer WS2 Eg ≈ 2.05 eV, Visible region


Applications in Optoelectronics
LED & Photovoltaic devices
Sample preparation (Top-down approach)

Probe Horn WS2 suspension in DMF DMF Suspended WS2 flakes


in Dimethyle Formamide
Structural Characterization
bulk WS
X-rays Diffraction from Crystalline WS2 2

(002)
Intense (002) peak indicates the
presence of layered structure
Intensity (a.u.)

(008)
(105)
(006)
(101)

(103)
(100)
(004)

(110)
(112)

(200)

(116)
(114)

(203)

(0010)
(102)

(107)
(106)
10 20 30 40 50 60 70 80
2 (degree)
X-rays Diffraction … continued
Calculation of lattice parameters:

For (002) plane:


Results matches
with JCPDS data

For (103) plane:


Raman active modes in TMDC’s (Theory)

Three modes due to in-plane motion of Chalcogen and W/Mo atoms


One mode due to out-of-plane motion of the chalcogen atom
Raman Spectra of Crystalline WS2

A1g mode due to out-of-plane vibrations of chalcogen atom


E2g1 mode due to relative motion of chalcogen atom and W
TEM images on WS2 samples
Nano-beam diffraction
(NBD) pattern from WS2
flakes

Confirms the crystalline


structure of the WS2

Six fold symmetry (3R-


polytype)

Flakes of WS2

Selected area e-beam diffraction (SAED)


pattern from WS2 flakes (after sonication)

Confirms that different layers are rotated


Optical Characterization
UV-Visible spectra of WS2 suspensions in DMF W5

0.014

2.25 eV
0.012

2.6 eV

3.0 eV
Direct bandgap point
0.010 1.91 eV
(h)(eV cm-1)

B C D
0.008 A

0.006

0.004

0.002

0.000
1.5 2.0 2.5 3.0 3.5
Energy (eV)

Two direct transitions (Bulk) at the Κ point occur due to the splitting of the valence band, and
leveled as excitons A (1.91 eV) and B (2.25 eV)

The peak C around 2.6 eV and D around 3 eV is recognized as the excitonic transitions from
multiple points near Γ point of the Brillouin zone
Photoluminescence from WS2 suspensions in DMF

Peaks at energy 1.51 eV and 1.44 eV are attributed to indirect band gap emission involving a
conduction band minimum at a midpoint between k and Γ points and valence band maximum at
the Γ point

The peaks at 2.6 eV and 2.94 eV is recognized as the excitonic transitions from multiple points
near Γ point of the Brillouin zone
Summary

• X-rays diffraction confirmed the presence of multilayer structure

• Raman scattering confirmed the presence of two modes (A1g and E12g)

• Electron beam diffraction pattern confirms the crystalline nature of sample. A


few layers are found to be rotated, resulting in ring pattern.

• UV-Vis measurements show 4 excitonic transitions. Two at K point arising


from Spin-Orbit Coupling splitted Valence Band and two at transition between
VBmaxima and multiple CBminima at Γ point .

• Observed PL emission due to excitonic states originating between CBminima


and VBmaxima (splitted due to Spin-Orbit coupling) at K point and excitonic
transitions from multiple points near Γ point.
Thanks
Brillouin Zone for monolayer WS2
W
S

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