Raman Spectroscopy, Theoretical Analysis, and Synthesis: From Two-Dimensional Semiconductor To Nanostructured Biochar

Raman spectroscopy, theoretical analysis, and
synthesis: from two-dimensional

semiconductor to nanostructured biochar
Raphael Longuinhos, Jenaina Ribeiro Soares*
Universidade Federal de Lavras (UFLA - Brazil)

2019/09/24
1
Summary
 2D materials: spectroscopic signature and strain in

GaSe;
• Low-frequency modes;
• Strain;
• Major findings
 Raman spectroscopy of carbonaceous materials with

soil science concern:
• Carbonaceous materials in anthropogenic soils;
• Biochar and biochar-based fertilizers;
• Major findings
 Acknowledgments 2
Graphene and beyond-graphene
materials: several possibilities
 2004: graphene experimental *
isolation;
Hexagonal boron nitride
 Possibility to explore other new
two-dimensional materials;
** Silicene, Germanene,
Stanene, Blue phosphorene
***
Black phosphorene
WS2
S
W
MX2 (transition metal
* Forster, F., et al. Physical Review B 88 (8)(2013): 085419. dichalcogenides) KCa2Nb3O10 (Peroviskite)
** Zhang, J., et al. Nano letters 11(6)(2011): 2407-2414. 3
*** Bizeto, M. A. et al. Journal of Materials Chemistry 19 (17) (2009): 2512-2525.
 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
1 1L
MoSe2 E2g 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)

2
(~40 nm) 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 2
A1g
1
A1g 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.
Low-frequency modes in layered nanostructures:
Metal monochalcogenide 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
10
11
Linear chain model *
**
* Tan, P. H., et al., Nature materials 11.4 (2012): 294 12

** Longuinhos, R. and Ribeiro-Soares, J. Phys. Chem. Chem. Phys., (2016), 18, 25401
 Elastic constants
13
Strain in monolayer GaSe
14
Longuinhos, R. and Ribeiro-Soares, Phys. Rev. Applied, (2019), 11, 024012
Strain in monolayer GaSe (without strain)
Raman Raman Raman Raman/Infrared Infrared Raman
15
Two-dimensional Young’s modulus
16
GaSe biaxial strain (bxy)
17
GaSe armchair and zigzag strain (ac, zz)
18
Non-degenerate modes: Degenerate modes:
Grüneisen parameter
Shear deformation potential
19
GaSe: major findings
 As good as or even betther lubricant than graphite;
 Distinguish β and ε polytypes;
 Strain-induced frequency shifts and symmetry lowering;
 Important mechanical and thermodynamic constants:
• 2D Young’s modulus:
o 2x softer than MoS2;

o 4x softer than graphene.
• Poisson’s ratio;
• Grüneisen parameter;
• Shear deformation potential.
 E’ and A1’ (also < 1%): soft material, frigile strain sensor applications!
Longuinhos, R. and Ribeiro-Soares, J. Phys. Chem. Chem. Phys., (2016), 18, 25401 20
Indian Dark Earths or “Terras Pretas de
Índios da Amazônia”
 Extremely fertile soils;
 High stability and resistance;
 Occupation by indians;
 Carbonaceous materials: up to 70X

more than in adjacent soils;
 Efforts: produce the “Terra Preta Nova”
B. Glaser et al. Naturwissenschaften 88, 31-41 (2001)

21
Raman spectroscopy of carbonaceous
materials
 D and G bands position, shape, and structural disorder
G band
D band
22
Adapted from A. C. Ferrari and J. Robertson. Phys. Rev. B 61 (20) (2000)
Nanographite from Diamond-like carbon
1
1
*
*MARSH, H.; RODRÍGUEZ-REINOSO,

F, Activated Carbon. Elsevier 2006
2
1L.G. Cançado et al. Appl. Phys. Lett. 88(16):163106 (2006) 23

2Tuinstra, F., and J. L. Koenig. The Journal of Chemical Physics 53(3) (1970): 1126-1130.
Carbonaceous content of Indian Dark
Earths: Raman spectroscopy
1
DLC samples
24
1Ribeiro‐Soares, J., et al. Journal of Raman Spectroscopy 44(2) (2013): 283-289.
Carbonaceous content of Indian Dark
Earths: Raman spectroscopy
25
1Jorio, A., et al. Soil and Tillage Research 122 (2012): 61-66.
a) b)
c)
26
Web of Science, 25/05/2019
“Biochar”
12º
27
Scopus, 25/05/2019
Synthesis, engineering and
characterization of Biochar
J. S. S. Carneiro et al. "Carbon stability of engineered biochar-based phosphate fertilizers." ACS Sustainable Chemistry & 28
Engineering 6.11 (2018): 14203-14212.
J. S. S. Carneiro et al. "Carbon stability of engineered biochar-based phosphate fertilizers." ACS Sustainable Chemistry & 29
Engineering 6.11 (2018): 14203-14212.
1600
1595
1590
-1
1585
G / cm
1580
1575
CF 900
1570 CF 550
CF 450
1565 CF 350
1560
55 60 65 70 75 80 85 90 95 100 105 110
-1
G / cm
1600
1595
1590
1585
-1
G / cm
1580
1575
1570 CF 350
COR 350
1565 VM 350
1560
55 60 65 70 75 80 85 90 95 100 105 110
T. R. L. Abreu et al. Submitted (2019) -1 30
G / cm
F. Rezende et al. In preparation (2019)
Biochar’s major findings
 Raman spectroscopy: carbonaceous materials in anthropogenic soils;
 Biochar and biochar-based fertilizers: tuning the disorder degree of

carbonaceous materials to improve soil quality;
 Raman and synthesis of carbonaceous nanomaterials: from basic

science to engineering of multifunctional materials.
31
Research group: NanoMat
http://jenainassoares2.wixsite.com/nanomat
 Nanomaterials and instrumentation
• New 2D materials;
• Biochar;
• Instrumentation.
32
Acknowledgments
> Prof. Dr. Raphael Longuinhos (DFI); > Prof. Dr. Carlos Alberto Achete;
> Prof. Dr. Paulo Fernando Trugilho (DCF); > Dr. Bráulio Soares Archanjo; > Prof. Dr. Ado Jorio de Vasconcelos;
> Prof. Dr. José Tarcísio Lima (DCF); > Prof. Dr. Luiz Gustavo Cançado;
> Dr. Erlon H. Martins Ferreira
> Prof. Dr. Leônidas Melo (DCS);
> Prof. Dr. Guilherme Ferreira (DQI);
> Dra. Fabiana Abreu de Rezende > Prof. Dr. Hugo Bonette de Carvalho.
33
Acknowledgments
 IOP Publishing: “Outstanding Reviewer for "2D Materials" (IF = 7.0)”;

 “For Women in Science” Loréal-Unesco-ABC (Physics, 2017): For her significant
contribution to research in Brazil;
 Honor Medal UFG 2017: alumni who have excelled by relevant contributions to34
the society in general.
Thank you!
http://jenainassoares2.wixsite.com/nanomat
35

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Raman spectroscopy, theoretical analysis, and

synthesis: from two-dimensional

Raphael Longuinhos, Jenaina Ribeiro Soares*

Universidade Federal de Lavras (UFLA - Brazil)

 2D materials: spectroscopic signature and strain in

 Raman spectroscopy of carbonaceous materials with

Raman Intensity (Arb. units)

Raman Intensity (Arb. units)

375 380 385 390 395 400 405 410 415

Raman Intensity (Arb. units)

* Tan, P. H., et al., Nature materials 11.4 (2012): 294 12

Raman Raman Raman Raman/Infrared Infrared Raman

Two-dimensional Young’s modulus

Shear deformation potential

 Distinguish β and ε polytypes;

 Strain-induced frequency shifts and symmetry lowering;

 Important mechanical and thermodynamic constants:

o 2x softer than MoS2;

 Extremely fertile soils;

 High stability and resistance;

 Carbonaceous materials: up to 70X

 Efforts: produce the “Terra Preta Nova”

B. Glaser et al. Naturwissenschaften 88, 31-41 (2001)

*MARSH, H.; RODRÍGUEZ-REINOSO,

1L.G. Cançado et al. Appl. Phys. Lett. 88(16):163106 (2006) 23

 Raman spectroscopy: carbonaceous materials in anthropogenic soils;

 Biochar and biochar-based fertilizers: tuning the disorder degree of

 Raman and synthesis of carbonaceous nanomaterials: from basic

 Nanomaterials and instrumentation

 IOP Publishing: “Outstanding Reviewer for "2D Materials" (IF = 7.0)”;

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