XIV B MRS Meeting Jenaina Final

Structural characterization of beyond-
graphene materials: from atomic

semiconductors to geology
Jenaina Ribeiro Soares*, Raphael Longuinhos
Universidade Federal de Lavras (UFLA - Brazil)

2021/09/01 1
Summary
 2D materials: spectroscopic signature in thin GaS and

jacutingaite/tilkerodeite systems;
• Structural information;
• Polarization dependence;
• Symmetry lowering in thin GaS films;
• Major findings for each case
 Additional related work
 Acknowledgments
2
Graphene and beyond-graphene
materials: several possibilities
 2004: graphene experimental isolation;
 Possibility to explore other new two-dimensional materials;
3
* Li, Xinming, et al. Applied Physics Reviews 4.2 (2017): 021306.
 Heterostructures, strain engineering, thickness, electric field…
*****
4
Churchill, H. O. H., and Jarillo-Herrero, P. Nature Nanotechnology 9(5) (2014): 330-331.
materials: spectroscopic signatures
Graphene G' TMDs (monolayer) MoS2
Raman Intensity (Arb. units)

TaSe2

5L
MoTe2 4L
G 3L
WSe2
WS2 2L
1L
MoSe2 E2g
1
A1g
MoS2 Bulk
375 380 385 390 395 400 405 410 415

1250 1500 1750 2000 2250 2500 2750 100 150 200 250 300 350 400 450 Raman Shift (cm-1)
Raman Shift (cm-1)
Raman Shift (cm-1)
Eg
2 Raman Shift (cm-1)
Sb2Te3
Black Phosphorus B2g
h-BN E2g Raman Intensity (Arb. units) (~40 nm) 2

A1g
1 2
A1g Ag
1
Eg 1
2
Ag
A1g Bulk
2
Eg A1u
Bi2Te3
Bulk (x 0.02) 1 1 3L
Eg A1g 2
(10 QL)
3L
Eg
2L
2L Bi2Se3
A1g
1
A1g
2
1L
1L (8 QL)
350 375 400 425 450 475
1300 1325 1350 1375 1400 1425 25 50 75 100 125 150 175 200
Raman Shift (cm-1)
Raman Shift (cm-1) Raman Shift (cm-1)
5
1
Several references: contact me at jenaina.soares@ufla.br for further information.
Tunable band gap with strain in Post-Transition
Metal Monochalcogenides (GaSe)
GGA-PBE HSE06
6
Huang, Le, Zhanghui Chen, and Jingbo Li. RSC Advances 5.8 (2015): 5788-5794.
 Heterostructures, strain engineering, thickness, electric field…
*****
GaSe,
InSe,
GaS,...
7
Adapted from: Churchill, H. O. H., and Jarillo-Herrero, P. Nature Nanotechnology 9(5) (2014): 330-331.
Since 2016: Metal monochalcogenides
Low-frequency modes in layered GaSe

β-GaSe ε-GaSe
**
8
*Longuinhos, R. and Ribeiro-Soares, J. Phys. Chem. Chem. Phys., (2016), 18, 25401
Low-frequency Raman or infrared modes in layered
nanostructures: Metal monochalcogenide GaSe
 Example: GaSe Shear Breathing
9
Longuinhos, R. and Ribeiro-Soares, J. Phys. Chem. Chem. Phys., (2016), 18, 25401
Strain in monolayer GaSe
10
Longuinhos, R. and Ribeiro-Soares, Phys. Rev. Applied, (2019), 11, 024012
GaSe armchair and zigzag strain (ac, zz)
11
Longuinhos, R. and Ribeiro-Soares, Phys. Rev. Applied, (2019), 11, 024012
TERS in GaS: The A1g intensities
Tip-Enhanced Raman Spectroscopy in GaS: A1g modes vs number of layers
12
Alencar, R. S., et al. Nano letters 19.10 (2019): 7357-7364.
Raman in GaS: dimensionality-induced
effects?
β-GaS
13
Alencar, R. S., et al. Physical Review B 102.16 (2020): 165307.
Raman in GaS: thin film characterization
AFM: 2, 3, 4, 10 and 53 layers (bulk)
14
Raman in GaS: Polarization-dependent
measurements
2, 3, 4, 10 and 53 layers (bulk)
15
parameters
16
parameters
Structural changes according to

the number of layers?
17
Raman in GaS: Structural changes according
to the number of layers
* Bulk β-GaS
* N odd layers β-GaS * N even layers β-GaS
18
Raman in GaS: Structural changes according
to the number of layers
* Bulk β-GaS
* N odd layers β-GaS * N even layers β-GaS
19
Raman in GaS: Experimental vs simulation
data
20
GaS: major findings
 Raman intensity polar dependence:
 New modes: symmetry lowering;
 DFT: good agreement;
 Structural changes: layer number identification, symmetry lowering (strain,

substrate, and so on);
 Key issues for applications
21
Jacutingaite: new platinum-group layered
mineral (Pt2HgSe3)
*
 2008: Itabira, Minas Gerais state, Brazil;
 2018: 1L, topological gap of ~ 0.5 eV;**
 “The most outstanding QSHI among

more than 1,000 novel 2D exfoliable
***
materials”;
****
 Isostructural to tilkerodeite (Pd2HgSe3);
 Structural information + fast and reliable

identification?
* Cabral, A. R., et al., Terra Nova 20.1 (2008): 32-37.

**Marrazzo, A., et al., Physical review letters 120.11 (2018): 117701.
***Mounet, N., et al. Nature nanotechnology 13.3 (2018): 246-252. 22
****Longuinhos, R., et al. Journal of Raman Spectroscopy 51.2 (2020): 357-365.
Jacutingaite: structural information
****
23
Longuinhos, R., et al. Journal of Raman Spectroscopy 51.2 (2020): 357-365.
Jacutingaite: experimental Raman spectra
24
Lattice phonon modes
R R 25
Raman mode assignments
R R
Parallel
Parallel and cross
26
Raman mode assignments
R R
Parallel
Parallel and cross
27
Raman mode wavenumber: experiments
vs simulation
28
Raman mode atomic displacements for
each mode
29
Jacutingaite vs tilkerodeite: different
mechanical properties

Longuinhos, R., et al. Journal of Physics: Condensed Matter 33.6 (2020): 065401. 30
Longuinhos, R., et al. Journal of Applied Physics 130.1 (2021): 015105.
Jacutingaite and tilkerodeite: major
findings
 Experimental and simulation Raman results: Jacutingaite (9 of the 11 modes),
tilkerodeite (11 modes);
 Symmetry mode assignment, selection rules;
 Atomic displacements and wavenumbers (several DFT functionals);
 Structural changes: symmetry lowering (turn on and of topological

properties?);
 Fundamental to the understanding of their electric, optical, mechanical and

thermal properties.
Longuinhos, R., et al. Journal of Physics: Condensed Matter 33.6 (2020): 065401. 31
Longuinhos, R., et al. Journal of Applied Physics 130.1 (2021): 015105.
Research group: NanoMat
http://jenainassoares2.wixsite.com/nanomat
 Nanomaterials and instrumentation
• New 2D materials;
• Biochar;
• Instrumentation.
32
Raman spectroscopy of carbonaceous
materials
 D and G bands position, shape, and structural disorder
G band
D band
33
Adapted from A. C. Ferrari and J. Robertson. Phys. Rev. B 61 (20) (2000)
Synthesis, engineering and
characterization of Biochar
Carneiro, J. S. S., et al. ACS Sustainable Chemistry & Engineering 6.11 (2018): 14203-14212.
Batista, G. A., et al. Acta Scientiarum. Technology 42 (2020): e45914-e45914.
34
Nardis, B. O., et al. Production of engineered-biochar under different pyrolysis conditions for phosphorus removal from aqueous
solution. Submitted.
Synthesis and characterization of new
2D materials
CVD MoS2: 1, 2, 3 layers, ~ 20 µm in lateral size, or film
35
Bernardo, E. C., et al. In preparation
Thank you!
http://jenainassoares2.wixsite.com/nanomat
36

XIV B MRS Meeting Jenaina Final

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Structural characterization of beyond-

graphene materials: from atomic

Jenaina Ribeiro Soares*, Raphael Longuinhos

Universidade Federal de Lavras (UFLA - Brazil)

 2D materials: spectroscopic signature in thin GaS and

 Additional related work

 Possibility to explore other new two-dimensional materials;

Raman Intensity (Arb. units)

Raman Intensity (Arb. units)

375 380 385 390 395 400 405 410 415

Raman Intensity (Arb. units)

Low-frequency modes in layered GaSe

Structural changes according to

* N odd layers β-GaS * N even layers β-GaS

* N odd layers β-GaS * N even layers β-GaS

 Raman intensity polar dependence:

 New modes: symmetry lowering;

 DFT: good agreement;

 Structural changes: layer number identification, symmetry lowering (strain,

 Key issues for applications

 2008: Itabira, Minas Gerais state, Brazil;

 2018: 1L, topological gap of ~ 0.5 eV;**

 “The most outstanding QSHI among

 Structural information + fast and reliable

* Cabral, A. R., et al., Terra Nova 20.1 (2008): 32-37.

Parallel and cross

Parallel and cross

Longuinhos, R., et al. Journal of Raman Spectroscopy 51.2 (2020): 357-365.

 Symmetry mode assignment, selection rules;

 Atomic displacements and wavenumbers (several DFT functionals);

 Structural changes: symmetry lowering (turn on and of topological

 Fundamental to the understanding of their electric, optical, mechanical and

 Nanomaterials and instrumentation

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