group theory for structural analysis and lattice vibrations in

Raman spectroscopy and symmetry

analysis for phonons in two-dimensional

materials

Jenaina Ribeiro [email protected]

Universidade Federal de Lavras (UFLA) -Brazil

1

Summary

Background

Recent works

• Carbonaceous materials in soils;

• Diamond-like carbon;

• New probes for AFM and TERS;

• Vibrational properties of new 2D materials

Conclusions2

Summary

Background

Recent works





Conclusions3

Background

4

Master’s degree and PhD (Brazil)

2009-2014

Exchange

program 2013-2014

Physics (theory/experiments)

Focus: Raman spectroscopy

Universidade Federal de Minas Gerais (UFMG)

Massachusetts Institute of Technology

Background

5

Now: Universidade Federal de Lavras (UFLA)

Lavras

Background

6

Now: Universidade Federal de Lavras

(UFLA)

Materials science (theory/experiments)

• New 2D materials

• Conductive polymers + nanomaterials

• Biochar Diêgo Silva Santos Ana Luiza Costa

Silva

Lorrana Bichoff Paulo Henrique

Carneiro dos Reis

+

Taís Regina Lima Abreu, Mariana Fukuda do Carmo

Leonardo Matile

Silveira

Students

Black phosphorene

Background

7

MITPenn State

University of Alabama

University of Cambridge

UFMG

UNIFALINMETRO

EMBRAPA UFLA

Collaboration network

?

Espectroscopia Raman

8

Raman spectroscopy

Stokes

Courtesy: L. G. Cançado

Summary

Background

Recent works





Conclusions9

Indian Dark Earths or “Terras Pretas de

Índios da Amazônia”

10

Extremely fertile soils;

High stability and resistance;

Occupation by indians;

Presence of carbonaceous materials:

substantial (up to 70 times more than in

adjacent soils);

Efforts: establish research guidelines

(produce the “Terra Preta Nova”);

Development of sustainable agricultural

practices.

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

111Ribeiro‐Soares, J., et al. Journal of Raman Spectroscopy 44(2) (2013): 283-289.

1

2

Carbonaceous content of Indian DarkEarths: Raman spectroscopy

DLC samples

2L.G. Cançado et al. Appl. Phys. Lett. 88(16):163106 (2006)

121Ribeiro‐Soares, J., et al. Journal of Raman Spectroscopy 44(2) (2013): 283-289.2Pagano, M., et al. Soil and Tillage Research 155 (2016): 298-307.

1

2


DLC samples

1


131Jorio, A., et al. Soil and Tillage Research 122 (2012): 61-66.

2Ribeiro‐Soares, J., et al. Journal of Raman Spectroscopy 44(2) (2013): 283-289.

1 2

Summary

Background

Recent works





Conclusions14

15

Structural analysis of polycrystalline graphene systems by Raman

spectroscopy:• Ribeiro-Soares, J. et al. Carbon 95, 646-652 (2015).

15

(e)

1000 1500 2000 2500 30001

10

100

1000

La (

nm

)

HTT (oC)

X ray

TEM

STM

1000 1200 1400 1600 1800

2800°C

2600°C

2400°C

2300°C

2200°C

2000°C

1800°C

1600°C

1400°C

1200°C

In

ten

sity (

arb

. units)

Raman shift (cm-1)

3.8 nm

4.6 nm

10 nm

17 nm

30 nm

58 nm

140 nm

217 nm

526 nm

2300 nm

(d)

10 100 1000

0.5

1.0

1.5

2.0

2.5

0 20 40 60 800

1

2

3

4

5

6

1.96 eV

2.33 eV

2.71 eV

I D /I G

La (nm)

C A

,SG

E4L (eV4)

1 10 100 10000

20

40

60

80

100

120

La (nm)

A G

(cm

-1)

1.96 eV

2.33 eV

2.71 eV

Diamond-like carbon

1616

(e)

1000 1500 2000 2500 30001

10

100

1000

La (

nm

)

HTT (oC)

X ray

TEM

STM

1000 1200 1400 1600 1800

2800°C

2600°C

2400°C

2300°C

2200°C

2000°C

1800°C

1600°C

1400°C

1200°C

In

ten

sity (

arb

. units)

Raman shift (cm-1)

3.8 nm

4.6 nm

10 nm

17 nm

30 nm

58 nm

140 nm

217 nm

526 nm

2300 nm

(d)

10 100 1000

0.5

1.0

1.5

2.0

2.5

0 20 40 60 800

1

2

3

4

5

6

1.96 eV

2.33 eV

2.71 eV

I D /I G

La (nm)

C A

,SG

E4L (eV4)

1 10 100 10000

20

40

60

80

100

120

La (nm)

A G

(cm

-1)

1.96 eV

2.33 eV

2.71 eV

General relation between the Raman spectrum and the

crystallite size in polycrystalline carbonaceous materials

Diamond-like carbon

Structural analysis of polycrystalline graphene systems by Raman

spectroscopy:• Ribeiro-Soares, J. et al. Carbon 95, 646-652 (2015).

Summary

Background

Recent works





Conclusions17

New probes for AFM and TERS

18* Patent: (21) BR 10 2012 033304-0 A2 “Dispositivo Maciço com extremidade unidimensional para microscopia e

espectroscopia óptica de campo-próximo”. Instituto Nacional da Propriedade Industrial - INPI (2012-2014)

*

2

19

New probes for AFM (encapsulated withcarbon nanocones)

2Patent: (21) BR 10 2012 026973-2 A2 “Dispositivo Maciço encapado com nanocone de carbono para microscopia e

espectroscopia por varredura de sonda”. Instituto Nacional da Propriedade Industrial - INPI (2012-2014)

1

1 Cano-Marquez, A. G. et al. Scientific Reports 5, 10408 (2015).

Colaborações em outros projetos

201 Cano-Marquez, A. G. et al. Scientific Reports 5, 10408 (2015).

New probes for AFM (encapsulated withcarbon nanocones)

Molecular dynamics simulations

Summary

Background

Recent works





Conclusions21

Graphene and beyond graphene

materials: several possibilities

22

2004: graphene mechanical

isolation;

Possibility to explore other new

two-dimensional materials;

* Forster, F., et al. Physical Review B 88 (8)(2013): 085419..

** Zhang, J., et al. Nano letters 11(6)(2011): 2407-2414.

*** Bizeto, M. A. et al. Journal of Materials Chemistry 19 (17) (2009): 2512-2525.

MX2 (transition metal

dichalcogenides)

S

W

WS2

KCa2Nb3O10 (Peroviskite)

Hexagonal boron nitride

Silicene, Germanene,

Stanene, Blue phosphorene

Black phosphorene

*

***

**



23

Heterostructures, strain engineering, thickness, electric field…

*****

Churchill, H. O. H., and Jarillo-Herrero, P. Nature Nanotechnology 9(5) (2014): 330-331.

Two-dimensinal phosphorus allotropes

24

New allotropes:Blue phosphorus (Blue

P). Expected bandgap: 2 eV (monolayer);

Other materials: Si (silicene), Ge

(germanene), Sn (stanene);

2Vogt, P. et al. Physi. Rev. Lett. 108(15) (2012): 155501.

1 Zhu, Zhen, and David Tománek. Physi. Rev. Lett. 112(17) (2014): 176802.

1

1

2



25

1250 1500 1750 2000 2250 2500 2750

2D

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

Raman Shift (cm-1)

G

Graphene

25 50 75 100 125 150 175 200

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

Raman Shift (cm-1)

A2

1g

E2

g

A1

1g

E1

g

A2

1g

E1

g

A1

1g

E2

g

A2

1g

E2

g

A1

1g

A1u

Sb2Te

3

(~40 nm)

Bi2Te

3

(10 QL)

Bi2Se

3

(8 QL)

1300 1325 1350 1375 1400 1425

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

Raman Shift (cm-1)

Bulk (x 0.02)

3L

2L

1L

E2g

h-BN

100 150 200 250 300 350 400 450

Raman Shift (cm-1)

Raman Shift (cm-1)

TaSe2

MoTe2

WSe2

WS2

MoSe2

MoS2

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

TMDs (monolayer)

375 380 385 390 395 400 405 410 415

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

5L

4L

3L

2L

Raman Shift (cm-1)

Bulk

1LA

1gE1

2g

MoS2

350 375 400 425 450 475

Black Phosphorus

A2

g

B2g

A1

g

Ra

ma

n I

nte

nsity (

Arb

. u

nits)

Raman Shift (cm-1)

1L

2L

3L

Bulk

1 Several references: contact me at [email protected] for further information.

mailto:[email protected]

26

Prospects about research in new 2D materials (ISI Web of Science 12-10-

2015);

1Adapted from Ribeiro-Soares, J., and M. S. Dresselhaus. Brazilian Journal of Physics 44.2-3 (2014): 278-282.

1

1965

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2010

2015

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600

'Transition metal dichalcogenides'

'Monolayer transition metal

dichalcogenides'

Pu

blis

he

d I

ten

s

Year

1965

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2015

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"Transition metal dichalcogenides"

"Monolayer transition metal

dichalcogenides"

Cita

tio

ns

Year


materials: scientific community interest

Group theory for structural analysis and lattice

vibrations in phosphorene systems

27

Structures: buckled graphene;

Group-subgroup relations: structural transitions;

Correlations among the Irreducible Representations (Irs): a guide for Raman and infrared

measurements

1

Ribeiro-Soares, J., et al. Physical Review B 91. (2015) 205421.



28

Mode eigenvectors for monolayer Black and Blue P (backscattering geometry):

Raman active

Infrared active

Silent1Ribeiro-Soares, J., et al. Physical Review B 91. (2015) 205421.



29

Applying a compressive strain in Blue P: expected Raman modes are different.

2

1Wang, Y. et al. Small 9(17) (2013): 2857-2861.

1

MoS2

2Ribeiro-Soares, J., et al. Physical Review B 91. (2015) 205421.



30

Lattice representations for N layer 1


Experimental data: Black Phosphorus

31

Experimental data1

1Favron, A., et al. "Exfoliating black phosphorus down to the monolayer: photo-induced oxidation and electronic

confinement effects." arXiv preprint arXiv:1408.0345 (2014).

Main features:

• Broadening of the Ag2 band for N<5;

• Shift of the Ag2 to higher frequencies;

• Evidence of more than one band in bilayer


vibrations in transition metal dichalcogenides

32

Ribeiro-Soares, J., et al. Physical Review B 90.11 (2014): 115438.



33




34




35

Brillouin Zone (BZ): analogous

graphene’s BZ;




36


Lattice vibration representations for bulk

TMDCs (1T and 2H polytypes) at all points in

the BZ

37Ribeiro-Soares, J., et al. Physical Review B 90.11 (2014): 115438.

Summary

Background

Recent works





Conclusions39

Conclusions and perspectives

40

Symmetry changes for transitions among structures;

Group theory for 2H and 1T TMDCs polytypes: more than 30 different

layered materials (MX2);

Symmetry variations are detected for different number of layers;

It is possible to predict the number of Raman and infrared active modes

and to identify them from experimental data;

Raman spectroscopy: characterization of carbonaceous content found

in soils;

Diamond-like carbons: Raman spectroscopy to study polycrystalline

samples;

Cooperation perspectives: theory + experiments in 2D nanomaterials

Thank you

41

group theory for structural analysis and lattice vibrations in

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