Loss Compensation in Optical Metamaterials Using Gain Media | Light | Fluorescence

Summer internship 2010

LOSS COMPENSATION IN OPTICAL METAMATERIALS USING GAIN MEDIA
Submitted byApoorv Balwani (071505) PST IV Yr Under the guidance of Dr. Giusseppe Strangi

AGENDA
Objective of today’s presentation is to affiliate the audience with the basic project undertaken by the trainee during the summer term 2010.  Discussions will be done on optical metamaterials, the various associated phenomenon and the polymer science aspect attached to it.

ABOUT EMPLOYER

The University of Calabria, situated in Southern Italy, is a public institution established in 1972. It is a medium-sized university with about 36,000 students, 800 teaching and research staff and about 700 administrative staff. It has six fully functional faculties of Economics, Engineering, Philosophy, Sciences, Pharmacy and Political science. LICRYL originates from the Liquid Crystal Group which operates since 1980 at the University of Calabria in the field of soft matter, being one of the pioneers in the field of material science.

ABOUT THE PROJECT
  

The Licryl lab is involved in a European collaboration, Metachem which aims at creation and development of metamaterials. The role of Licryl is to conduct practical experiments on samples sent and suggest feedbacks for improvement in the materials. At present, the focus is on reducing the optical losses faced in gold nanoparticles to produce metamaterials with unusually high levels of transparency. This is to be done by use of gain media, which in this case are fluorescent dyes which can transfer energy at optical wavelengths to the gold nanoparticles. The aim of this project was to learn and conduct these experiments in the lab and also attempt to transfer a uniform layer of these nanoparticles on polymeric substrates to obtain a thin film for testing in solid phase.

LOSS COMPENSATION IN OPTICAL METAMATERIALS USING GAIN MEDIA
Loss compensation (and resulting enhancement of transmission and scattering) by using gain media

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation

LOSS COMPENSATION (AND RESULTING ENHANCEMENT OF TRANSMISSION AND SCATTERING) BY USING GAIN MEDIA       Ethanol. both samples showed at least 3-4 times increase in intensity of transmitted light for very miniscule quantities of energy pumped into the system. . Nanoparticle solution was washed with fluorescent dyes and the sample was subjected to a pump-probe system of Nd-YAG lasers to test the magnitude of loss compensation and activation energies for various FRET phenomena. shape and composition. The underlying theory was confirmed with the data. In effect. the threshold energy in case of Bordeaux samples was lesser. toluene or chloroform based solution of gold nanoparticles was used as a primitive metamaterialistic system. Probes used were both monochromatic light as well as broadband light. Samples were received from various labs and had varied parameters in terms of size. While Bari samples showed higher magnitude of enhancements.

OPTICAL METAMATERIALS   Ever since the emergence of Veselago’s paper on left handed materials in 1968[1]. “A metamaterial is an artificially structured material which attains its properties from the unit structure rather than the constituent materials. and presented the required parameters for a material to achieve such systems. where the vectors E. the scientific community has been abuzz with curiosity and deeper research in the field of what is now called Metamaterials. which explored the extraordinary scenario. H and k form a left handed system. a development that could help form the basis for higher resolution optical imaging and nanocircuits for highpowered computers . A metamaterial has an inhomogeneity scale that is much smaller than the wavelength of interest.” – Cai & Shelev An engineered 3-D metamaterial that can reverse and bend the natural direction of visible and near-infrared light. and its electromagnetic response is expressed in terms of homogenized material parameters.

OPTICAL METAMATERIALS  The scientific community effectively converges on the following basics points which describe the nature of metamaterials: they have “properties unlike any natural substances”  they are synthesized by human beings  they exhibit exotic electromagnetic properties at optical frequencies which can be tailored as per wish  the order of inhomogeneity in the material is smaller than the wavelengths of interest  .

EXPERIMENTAL SETUP .

The basic idea behind the experiment is to use dyes with emission bands/spectra that considerably overlap the Surface Plasmon absorption spectra of the gold nanoparticles. . This chromophore. it emits energy in form of light (radiative transmission). This phenomenon is known as Forster’s Resonance Energy Transfer (FRET) and forms the foundation of this experiment. when placed in vicinity of another chromophore (capable of accepting the energy) at distances less than the wavelength of light emitted. FRET occurs in the most efficient manner. so that at distances in the order of nanometers. transfers energy to the adjacent particle in a non-radiative manner through dipole coupling.THEORY   When a chromophore is excited.

In theory. The spectroscopic results were noted. units) Step 1: The donor chromophorefluorescent dye chosen was C-500 (Cumarin 500) which has a fluorescent emission peak at around 506 nm and activation energy at around 320 nm. 5 506 nm 4 Abs_sample_S1 3 2 1  0 450 480 510 540 570 600 630 660 690 720 750 780 810 Wavelength (nm) . This value was close to the plasmon resonance peak of gold nanoparticles (nanospheres). it was expected that a fraction of light was absorbed by the gold nanoparticles to form localized Plasmon waves.THEORY  Fluorescence (arb. both transmitted as well as scattered light was of lower intensity than that expected from a totally transparent material. Thus. which was around 520 nm. Probe light was shined at 532 nm (green light).

This theory was consolidated by the various experiments carried out on the nanoparticles which have been described in later chapters with results. this energy was absorbed by the nanoparticles at LSPR (localized surface Plasmon frequency). the particles had become more transparent. In other words. the pump beam at 320 nm was directed at the sample. and emit fluorescent light at 506 nm. This caused the dye to activate. Due to FRET. . which lead it to transmit more energy at than wavelength. we see that the value of transmitted light as well as scattered light observed had increased considerably. Thus by using a system in which a dye activated at certain energy and cause FRET at a different energy.THEORY   Step 2: Next.

OBSERVATIONS.BARI SAMPLES  The samples received from Bari were cylindrical nanorods. they had LSPR on two different surfaces (radial & cylindrical) with different resonance frequencies . Thus in effect.

OBSERVATIONS. wherein a distinct. .BARI SAMPLES  The dye was mixed in the solution and the dye particles thus transmitted energy both radiatively as well as through FRET. sharp peak at probe wavelength was observed in a background of what is the fluorescent spectroscopy of the dye particles (due to residual fluorescence). This resulted in a graph of intensity v/s wavelength observed on the spectrometer.

BARI SAMPLES .OBSERVATIONS.

BARI SAMPLES    This meant that the fluorescence of the sample would decrease when the pump was switched on (with probe beam off). In this certain quenching experiment. quenching effect was seen by measuring fluorescence of solution containing only dye particles. This effect is known as quenching and the graphs depicting the effect are given on the following page. proving that this fluorescent energy was utilized for FRET. The quenching effects at each energy was noted and plotted using two curves on the following pages.OBSERVATIONS. . It was seen than the effect of quenching increased with increasing pump energy. and then fluorescence of solution containing both dye and nanorods (B2) was noted at the same energy. The reduction in intensity at every wavelength (or quenching) was also plotted.

The quenching effect graph is seen to closely match the trends of intensity v/s pump energy graphs obtained by the researchers for Rayleigh scattering and transmission experiments on the same sample prior to commissioning of the internship. this is close to the emission spectrum of the dye in use. . This suggests that while the increase in quenching with energy is rapid. As shown before.BARI SAMPLES    The quenching effect. the increase in fluorescence of the dye is also rapid enough to prevent an exponential rise in transmission.OBSERVATIONS. Also the maximum quenching is seen at around 497-500 nm. while the % quenched values vary linearly with the energy. measured by subtracting the intensities of fluorescence in dyes and B2 is seen to follow a slightly exponential curve.

BARI SAMPLES  Quenching of dyes .OBSERVATIONS.

BARI SAMPLES  Quenching of dyes .OBSERVATIONS.

BARI SAMPLES  Quenching of dyes .OBSERVATIONS.

BARI SAMPLES  Quenching of dyes .OBSERVATIONS.

BARI SAMPLES  Quenching of dyes .OBSERVATIONS.

BARI SAMPLES  Quenching effect dependence on pump energy .OBSERVATIONS.

OBSERVATIONS.BARI SAMPLES  Quenching effect dependence on pump energy .

BARI SAMPLES  Broadband measurements .OBSERVATIONS.

OBSERVATIONS.BARI SAMPLES  Broadband measurements .

the efficiency of the dye seems to vary with varying wavelengths.OBSERVATIONS.BARI SAMPLES  Broadband measurements  As can be seen from the graph.  The threshold energy also seems to decrease with increasing probe wavelength. thus highlighting the significance of overlapping fluorescence spectrum with the absorption spectrum of sample. which the trainee (self) was unable to account for or relate to. . It is typically found to be more efficient for lower wavelengths.

BARI SAMPLES  Conclusion  Thus the experiments yielded positive results in increasing transparency of the sample.OBSERVATIONS. with enhancements of as much as 8 times witnessed due to FRET. .

thus preventing any residual fluorescence. Au Core 12 ± 2 nm C500 in shell Silica Shell 12 ± 5 nm .OBSERVATIONS.BORDEAUX SAMPLES  These samples consisted of gold nanoparticles enveloped by a silica shell. The dye particles were embedded inside the Si shell.

OBSERVATIONS. units) 506 nm 4 Abs_sample_S1 3 2 1 0 450 480 510 540 570 600 630 660 690 720 750 780 810 Wavelength (nm) . 5 Fluorescence (arb.BORDEAUX SAMPLES  The absorption spectroscopy of ethanol solution of these particles showed a single peak at around 520 nm.

0 6.5 7.0 0.BORDEAUX SAMPLES  Rayleigh scattering  Similar trends as in bari samples were obtained.5 2.0 2. Scattered Intensity (arb.5 4.0 3.5 6.5 1.5 5.0 4.5 0.5 3. units) 20 18 16 14 12 10 8 6 4 2 Enhancement of SPs of gold Core-Shell Nps with C500 in the shell sample S1 (threshold 0.0 5.0 1.0 Pump Energy (mJ) .OBSERVATIONS.75mJ) -0.

 Also.BORDEAUX SAMPLES  Rayleigh scattering  Comparisons with previous study however found that the threshold energy in this case was significantly higher.OBSERVATIONS. . results varied significantly on various samples of the same Bordeaux make. which varied only in exposure to room temperatures.

0 0.0 0.5 5.0 2. S2 was a relatively fresh sample.5 6.5 1.5 3. while S1 had a more prolonged exposure to room temperatures Scattered Intensity (arb.0 1.5 0.0 2.5 4. units) Scattered Intensity (arb.0 3.75mJ) 35 30 25 20 15 10 5 -0.5 Pump Energy (mJ) Pump Energy (mJ) .0 1.5 2.BORDEAUX SAMPLES  Rayleigh scattering  In the two compared graphs shown.5 7.5 1.0 4. units) 20 18 16 14 12 10 8 6 4 2 Enhancement of SPs of gold Core-Shell Nps with C500 in the shell sample S1 (threshold 0.5 2.5 3.0 6.0 5.0 3.OBSERVATIONS.5 Enhancement of SPs of gold Core-Shell Nps with C500 in the shell sample S2 (threshold 0.0 0.66mJ) -0.

units) 12 10 8 6 4 Peak of transmission of a probe beam @ 532nm sample S2 (threshold 0.5 2.BORDEAUX SAMPLES  Rayleigh scattering  Transmission studies showed a similar curve.OBSERVATIONS.0 1.0 Pump Energy (mJ) .0 0. and consequentially.25 mJ) The enhancement in transmission however was no more than 3-4 times.5 1. 0. lower threshold energy. considerably lesser magnification compared to Bari samples. 14 Intensity (arb. but with a steeper slope. This was again conducted on a fresh sample.

0 1.4 1.8 1.8 0 1 2 3 4 5 6 Energy (mJ) .0 0.4 2.2 @ 490 @ 500 @ 510 @ 520 @ 540 Intensity (arbit) 2.BORDEAUX SAMPLES  Broadband experiments 2.OBSERVATIONS.2 1.6 1.

. however.OBSERVATIONS. The inclusion of analysis of Intensity jump (similar to the study of quenching effect in Bari samples). The behavior and trend of increase in enhancement of intensity can be treated analogous to what we observed in quenching of the fluorescent dyes.BORDEAUX SAMPLES  Conclusion  Thus we observe a similar trend in the Bordeaux samples as that obtained in the Bari samples. throws more light upon the nature of enhancement.

for practical purposes. Hence. . Preliminary tests revealed that a silicone. it can be well seen that solid systems alone can provide the durability and portability for the applications in optical fields. transfer of gold nanoparticles over solid substrates in forms of thin films was attempted and the functionality of the samples tested. The substrates used were made of polymer or glass.PDMS made as a successful base for the nanoparticles. The methods of transfer were pretty much primitive. Further tests on the optical characteristics are ongoing.Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation       The preliminary tests of the gold nanoparticles-solvent systems proved successful in terms of loss compensation and enhancement of optical properties. however the results revealed the possibility of a successful solid substrate based gold nanoparticle system. However.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Experiments: The part two of project aimed at creating a very thin film of nanoparticles on a solid substrate. and the methods of film creation. The experiments conducted to find the optimum solid substrate-nanoparticle system varied in the material used for the substrate. Based on these parameters. the following experiments were conducted:  Solvent evaporation on glass  on PDMS     Spin coating with NOA 61 Plasma polymerization Sandwich samples .

This brought a huge possibility (by forming Si-O-Si bonds) for the gold nanoparticles to adhere to the surface of other silica based substances. At the same time Bordeaux samples came with a coating of silica around the particles.Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Solvent evaporation: Ethanol is a very volatile solvent. For this reason. . Glass and PDMS were used.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation On glass  Although SEM results were nonconfirmatory on glass. We also obtained an absorption spectroscopy that confirmed presence of gold nanoparticles (also confirmed by the reddish tinge on the glass surface).  . we did obtain a uniform but low density image on high contrast background ITO.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On glass .

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On glass .

The uniform layers were however discontinuous and mostly clustured. A very uniform and dense layer was obtained on the sample.Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On PDMS    Poly (dimethylsiloxane) or PDMS is a type of transparent silicone which is UV resistant and has many favorable properties for optical and laser applications. with the exception of destabilizing the system at higher energies. The preliminary transmission tests also to an extent replicate the GNP-solvent results. . . A prolonged exposure to high energy laser was also found to permanently damage the system.5 mm and 1 mm) and filled with Serge samples and left to dry. Four 1 mm by 1mm cross sections were made with varying depths ( .25 mm. These instabilities can be a result of laser ablation of gold nanoparticles. as confirmed by the SEM images.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On PDMS .

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On PDMS .

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  On PDMS The preliminary transmission tests also to an extent replicate the GNP-solvent results. . These instabilities can be a result of laser ablation of gold nanoparticles. with the exception of destabilizing the system at higher energies. A prolonged exposure to high energy laser was also found to permanently damage the system.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Spin Coating  Spin coater is a device that is used to spread a liquid layer of the solution on a surface using the principle of centripetal force. and also with NOA 61 .  The coating thickness can be varied by varying the angular speed of the coaters. spin coater was used on previous experiments.  To eliminate the problem of discontinuous nonuniform layers.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation .

This mixture was then sonicated at elevated temperatures to decrease the viscosity of the emulsion as NOA 61 is thixotropic in nature. Absorption spectroscopy suggests the optimum results being obtained with spin coating values near that of sample C as seen in the next slide. three parts by volume of NOA 61 were mixed with one part of gold nanoparticles solution with ethanol. This emulsion was used to coat four different samples of ITO glass which differed in the angular speed and the time of spinning to give spin coats of different thicknesses. . First.Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation      NOA 61 is an optical adhesive consisting mainly of polymercaptoesters and was used as a polymer linker as well as to provide a substrate for the gold nanoparticle system.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Spin coating .

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Plasma polymerization .

now agglomerated into micronparticles. the PANI casing on the spherulites proves the ability of the process of forming stable systems.  .Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation Plasma polymerization  The globules obtained are those of gold particles. covered on the sides by PANI. The test is inconclusive in the sense of obtaining nanoparticulate behavior of gold. However.

.Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Sandwich samples The preliminary tests on absorption spectroscopy came out to be positive for a successful preparation of GNP-solid substrate systems.

Creation of gold nanoparticles-polymer systems and preliminary study of loss compensation  Conclusion  As shown. . Preliminary tests also supported the success of the experiment. Further tests are necessary to see if all the criteria of the tests are met and the systems can act as metamaterials. various GNP-substrate systems were created and found to be stable to various degrees.

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