Random laser properties in acrylate

polymers doped with xanthene dye and

single-walled carbon nanotubes
IFSC-USP

Adriano J. G. Otuka1 , Paulo H. D. Ferreira2 , Cleber R. Mendonça1 and

Leonardo De Boni1

1
Instituto de Física de São Carlos, Universidade de São Paulo, Brazil Fotônica
2
Departamento de Física, Universidade Federal de São Carlos, Brazil

www.photonics.ifsc.usp.br
 Outline
 I – Introduction

 II – Applications and Motivation

 III – Methods and Materials

 IV – Experimental techniques

 V – Results

 VII – Conclusions
 What is Random Laser?
A Conventional Laser

Gain Medium
 I – Temporal coherence

 II – High Spatial coherence

Optical Cavity

Credit: Science Magazine & Robert Tandy

A. Douglas Stone Research Group
Yale University
 What is Random Laser?
A Random Laser
 I – High Temporal coherence

 II – Low Spatial coherence

Characteristics

Coherent

Gain Medium and Scattering Centers

Incoherent

Amplification of
Credit: Science Magazine & Robert Tandy
A. Douglas Stone Research Group stimulated emission (ASE)
Yale University
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

C. T. Dominguez, R. L. Maltez, R. M. S. dos Reis, L. S. A. de

Melo, C. B. de Araújo, and A. S. L. Gomes, "Dependence of
random laser emission on silver nanoparticle density in PMMA
films containing rhodamine 6G," J. Opt. Soc. Am. B 28, 1118-
1123 (2011)
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

Q. Song, S. Xiao, Z. Xu, V. M. Shalaev, and Y. L. Kim, "Random

laser spectroscopy for nanoscale perturbation sensing," Opt.
Lett. 35, 2624-2626 (2010)
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

D. S. Wiersma and S. Cavalieri. "Light emission: A

temperature-tunable random laser," Nature. 414, 708 (2001)
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

A. Mermillod-Blondin, H. Mentzel, and A. Rosenfeld, "Time-

resolved microscopy with random lasers," Opt. Lett. 38, 4112-
4115 (2013)
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

J. Dubois and S. la Rochelle, “Active cooperative

tuned identification friend or foe (ACTIFF)” US Patent
5 966 227 (1999)
 Random Laser: Several Applications

• Optical applications;
• Spectroscopy;
• Temperature sensing;
• Time-resolved microscopy;
• Military applications;
• Medical diagnosis.

R. C. Polson and Z. V. Vardeny, "Random lasing in

human tissues," Appl. Phys. Lett. 85, 1289-1291 (2004)
 In this work:

Can we What we can see

Random laser properties in acrylate polymers

doped with xanthene dye and

single-walled carbon nanotubes

and artificially generating scaterring centers

 Standard Sample
Acrylate Monomers – Sartomer

(tris(2-hydroxyethyl)isocyanurate (ethoxylated(6) trimethyl-lolpropane triacrylate)

triacrylate)

Hardness to final structure Reduce shrinkage upon polymerization

Photoinitiator – Basf/Igarcure Xanthene Dye – Sigma Aldrich

Lucirin TPO-L Rhodamine B

1.2

0.8

A bsorban ce

0.4
Organic compound responsible to
start the photopolymerization
0.0
200 400 600 800
W avelength (nm )
Mixing and polymerizing
 Increasing Scattering Centers
Bulks polymerized with UV lamp (365nm) for 1h. AFM Images
without SWCNT

Scattering centers are formed by the mixture of

the two monomers acrylates.

0.01wt% Rhodamine B
‘

or

with SWCNT
0.01 wt% Rhodamine B + 0.01wt%SWCNT

SWCNT
(diameter = 5mm Sigma Aldrich
and height = 1mm)

SWCNT functionalized with carboxylic acid

number of scattering center is

increased
 Increasing Scattering Centers
How to increase the scattering centers artificially

(diameter = 5mm and height = 1mm) 0.01wt% Rhodamine B

or
0.01 wt% Rhodamine B + 0.01wt%SWCNT
Femtosecond Laser Writing

NA
0.65
(diameter = 5mm and height = 1mm)

technique
To be tested on the RL experimental setup
 Experimental Setup
Oscilloscope Random Laser Setup
3 Hz
Pulse Train Single Pulse up to 800 Hz

Off On
Computer

Nd:YAG Q-Switch Pockels Cells Mirror

Mode-Locked
 =532 nm
mW Power Control
Ocean Optics y
, Beam Splitter
Collinear x
Detection
Sample
z Mirror

Cylindrical
Spherical
Perpendicular Lens
Lens Reference
Detection Detector
 Experimental Setup
Random Laser Setup
0.5 nm resolution
Collinear Excitation
Spectrometer

Side View Optical fiber

Transversal Excitation 1 mm diameter
Spectrometer

Scan the conical

emission or
focus all light on
the optical fiber

Some characteristics of the RL emission depends on how the excitation is done

 Results: Collinear Detection
Acrylate Polymer: Rhodamine B
without SWCNT

AFM Images
Emission spectrum as function of pump energy

Multiples peaks

1 nm at Full Width Half Maximum

Coherent
Random Laser
emission
 Results: Collinear Detection
Acrylate Polymer: Rhodamine B

Emission intensity as function of pump energy

Integrating the curve
10.0

4
O utput Intensity (unit. arb.) - x10
7.5

5.0

2.5

0.0
0.0 1.5 3.0 4.5
E nergy ( J)
 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + SWCNT
SWCNT functionalized with carboxylic acid

Coherent
Random Laser
emission

AFM Images
Emission spectrum as function of pump energy

Multiples peaks

1 nm at Full Width Half Maximum

Coherent
Random Laser
emission
 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + SWCNT

Emission intensity as function of pump energy

Integrating the curve
3

4
Output Intensity (unit. arb.) - x10
2

0
0.0 1.5 3.0 4.5
E nergy ( J)

threshold energy is increased

 Results: Perpendicular Detection
Acrylate Polymer: Rhodamine B
Emission spectrum as function of pump energy
Perpendicular Excitation

50.0 6
O utput Intensity (unit. arb.) - x10

5
Linew idth - FW H M (nm )

37.5
4 Change on the emission behavior
3
25.0 Incoherent
2 Random Laser
12.5 emission
1

Amplification of
6

0.0 0
0.0 1.5 3.0 4.5
stimulated emission
E nergy ( J)
 Results: Perpendicular Detection
Acrylate Polymer: Rhodamine B + SWCNT
Emission spectrum as function of pump energy
Perpendicular Excitation

60 4
Output Intensity (unit. arb.) - x10

3
Linewidth - FW HM (nm )

40
Change on the emission behavior

2
Emission blue shifted of about 5 nm
20 Incoherent
1 Random Laser
emission
0
6

0
0.0 1.5 3.0 4.5 Amplification of
E nergy ( J) stimulated emission
 Increasing Scattering Centers
Increase scattering centers artificially

(diameter = 5mm and height = 1mm) 0.01wt% Rhodamine B

or
0.01 wt% Rhodamine B + 0.01wt%SWCNT
Femtosecond Laser Writing

NA
0.65
(diameter = 5mm and height = 1mm)

technique
 Experimental Setup
Femtosecond Laser Fabrication

CCD
Camera

Pulse
Picker
Femtosecond Laser
Mirror
50-fs; = 800 nm;
5.1 MHz

Beam Expander
Translational
Stage
NA
y 0.65

Sample
z x Computer

White Light
 Sample
Micromachined Sample

Optical Image

with and without

SWCNT

Confocal Image
Scattering Center Size: 4 µm
Distance between Scattering Centers: 9 µm
 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + Grid
Emission spectrum as function of pump energy

Coherent
Random Laser
emission

Emission spectrum as function of pump energy

Multiples peaks

1 nm at Full Width Half Maximum

Peaks are wavelength locked

Is it a RL or a
Feed Back Laser
 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + Grid

Emission intensity as function of pump energy

Integrating the curve

Emission spectrum as function of pump energy

 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + SWCNT + Grid

Coherent
Random Laser
emission

AFM Images
Emission spectrum as function of pump energy

Multiples peaks

1 nm at Full Width Half Maximum

Peaks are wavelength locked

 Results: Collinear Detection
Acrylate Polymer: Rhodamine B + SWCNT + Grid

Emission intensity as function of pump energy

Integrating the curve
3

4
Output Intensity (unit. arb.) - x10
2

0
0.0 1.5 3.0 4.5
Energy ( J)
 Results: Perpendicular Detection
Acrylate Polymer: Rhodamine B + Grid
Emission spectrum as function of pump energy
Perpendicular Excitation

50.0 0.6
O utput Intensity (unit. arb.) - x10

0.5
37.5
Linew idth - FW H M (nm )

0.4 Change on the emission behavior

25.0 0.3 Incoherent

0.2
Random Laser
12.5 emission
0.1

Amplification of
6

0.0 0.0
0.0 1.5 3.0 4.5 stimulated emission
E nergy ( J)
 Results: Perpendicular Detection
Acrylate Polymer: Rhodamine B + SWCNT + Grid
Emission spectrum as function of pump energy

60 0.5
O u tp u t In te n sity (u n it. a rb .) - x10

0.4
Lin e w id th - F W H M (n m )

40 Change on the emission behavior

0.3

0.2
Emission blue shifted of about 5 nm
20 Incoherent
0.1 Random Laser
emission
0 0.0
6

0.0 1.5 3.0 4.5 Amplification of

E nergy ( J)
stimulated emission
 Conclusions
Collinear Detection
To all configurations
Coherent Random Laser emission

Multiple peaks with SWCNT

without SWCNT Increase in the number of multiple peaks
Outside Grid

Peaks are wavelength locked

Inside Grid
 Conclusions
Perpendicular Detection
Incoherent Random Laser emission
Outside Grid Outside Grid
50.0 6 60 4

O utput Intensity (unit. arb.) - x10

O utpu t Intensity (unit. arb.) - x10
5
Linew idth - F W H M (nm )

Linew idth - F W H M (nm )

37.5 3
4 40

25.0 3 2

2 20
12.5 1
1

6
6
0.0 0 0
0.0 1.5 3.0 4.5 0.0 1.5 3.0 4.5
Energy ( J) Energy ( J)

Inside Grid Inside Grid

50.0 0.6 60 0.5
O utput Intens ity (unit. arb.) - x10

without SWCNT with SWCNT

O utput Intensity (unit. arb.) - x10

0.5
0.4
37.5
Linew idth - F W H M (nm )

Linew idth - F W H M (nm )

0.4 40
0.3
25.0 0.3
0.2
0.2 20
12.5
0.1
0.1
6

0.0 0.0 0 0.0

6
0.0 1.5 3.0 4.5 0.0 1.5 3.0 4.5
Energy ( J) Energy (J)
 Acknowledgments
Team
Prof. Cleber R Mendonça
Prof. Lino Misoguti
Adriano Otuka
Dr. Marcos R Cardoso
Franciele R Henrique
Gustavo Almeida
Prof. Vinicius Tribuzi
Jessica Dipold
Prof. Paulo H. Ferreira
Nathália Tomázio
Dr. Daniel S Correa
Ruben Fonseca
Fernando Gotardo
Oriana Avila
Renato Martins

Lucas Sciutti
Andre Tedeschi

Dr. Juliana Almeida

Dr. Jonathas Siqueira

www.fotonica.ifsc.usp.br