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Energy Transfer and Optical Anisotropy in Semiconducting PolymersSona N Avetian (6984974) 12 August 2019 (has links)
<p>To fully optimize devices
for solar energy conversion, a comprehensive understanding of how excitons
migrate in materials for solar cell devices is crucial. Understanding the
mechanisms behind exciton diffusion and energy transfer will enable the
fabrication of highly efficient devices. However to thoroughly study exciton
properties, techniques implementing high spatial (nm sizes) and temporal (fs
time scales) resolution is required. Herein, we utilize transient absorption
microscopy (TAM) with 50 nm spatial resolution and 200 fs temporal resolution
to elucidate exciton diffusion in polymeric materials for solar energy
conversion.</p>
<p>While organic devices are
inexpensive and require simpler fabrication procedures than inorganic
materials, their device efficiencies often suffer due to their semi-crystalline
nature, lending to short diffusion lengths which lead to trap sites and inevitably
recombination. It has been demonstrated that achieving long-range exciton diffusion
lengths is possible through coherence effects. Coherence can be found in an
intermediate electronic coupling region where delocalization and localization compete.</p>
<p>To exploit coherence effects,
we study polymeric systems in which polymer chains are highly aligned via
simple and scalable procedures; semiconducting fibers and solution coated films.
In studying the fiber, we first implement polarized photoluminesce (PL) to
determine optical ansitropy. From the polarized PL and PL images, it is
observed that emission intensities are largest when probing along the transition
dipole moment of the polymer. This suggests a type of Förester Resonance Energy Transfer mechanism
in which excitons hop from one polymer chain to another.</p>
<p>Solution coated polymer films
are also studied to understand exciton diffusion as a function of deposition
methods. By varying the solution concentration as well as coating rate, we are
able to tune the morphology of the film. We observe a strong dependence between
diffusion constant and deposition parameters, with diffusion constants of <i>ca.</i> 9, 13 and
33 cm<sup>2</sup>/s for three different films. The results obtained in this thesis are
preliminary steps in an effort to elucidate energy transfer mechanisms and rates.</p><br>
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Polytriarylamines containing fused ring and heterocyclic structures prepared using N-heterocyclic carbene complexes of palladiumSprick, Reiner Sebastian January 2013 (has links)
For the preparation of semiconducting polymers often ‘standard’ catalytic systems are used without further optimisation. New ligands, such as N-heterocyclic carbenes have shown excellent activity in cross-coupling reactions (e.g. Suzuki-Miyaura reaction, or Hartwig-Buchwald amination). These systems show excellent conversions under mild conditions and even allow the use of aryl chlorides as reagents. Nevertheless, previously no system has been reported for the synthesis of conjugated polymers, e.g. the Suzuki polycondensation or Buchwald-Hartwig type polycondensation using these catalysts. A NHC-Pd based catalytic system was optimised for a polyamination reaction and the catalyst [(IPr)Pd(allyl)Cl] was found to be the most active. Polytriarylamines were synthesised using the optimised catalytic system and tested in organic field-effect transistors. Mobilities found were low which was found to be attributed to the presence of high molecular weight fractions. Molecular weights were controlled using an in situ end-capping approach and polymers tested in the semiconducting layer of OFETs gave similar mobilities tothose reported earlier. Several polytriarylamines, which have not been reported previously, were synthesised using NHC-chemistry and the in situ end-cappingapproach, as well as polytriarylamines that have been reported previously using Pd/phosphine catalysts. One library containing polymers based on biphenyles andbridged biphenyles and another library containing polymers with bridged oligoarenes were synthesised. Suzuki polycondensation was also studied besides the polyamination protocol and low catalyst loadings and reaction temperatures could be realised using a NHC-Pd catalyst. Sulfur containing monomers that could not be polymerised using the polyamination were polymerised successfully. All polymers were fully characterised and studied as the active layer in organic field-effect transistors. The highest mobilities determined for these polymers (~10-2 cm2/Vs) is close to the highest reported for this class of polymer reported to date.
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PHOTOACOUSTIC IMAGING IN THE NIR-II WINDOW USING SEMICONDUCTING POLYMERSJiayingzi Wu (8727825) 19 April 2020 (has links)
<p><a>Molecular imaging revolutionized the way researchers and
clinicians visualize and investigate complex biochemical phenomena, and it is
beneficial </a><a>for
disease diagnosis, drug design and therapy assessment</a>. Among a variety of different imaging
techniques, the non-ionizing and non-invasive photoacoustic (PA) imaging is
attracting increased attentions, owing to its high spatial and temporal
resolutions with reasonable penetration depth in tissue. Parallel efforts have
been the preparation of PA imaging agents which has high PA efficacy and can
specifically label the targets at cellular or molecular level. Particularly,
there is exponentially growing interest in imaging in the
second near-infrared (NIR-II) window (1000–1700 nm), where offers
reduced tissue background and improved penetration depth. However, study of PA imaging
in the NIR-II window is incomplete, partly due to the lack of suitable
materials. Therefore, in my dissertation work I studied NIR-II PA imaging
through semiconducting polymer. </p>
<p>Firstly, the performance of PA imaging in the
NIR-II window is explored by using a semiconducting
polymer nanoparticle (SPN) which has strong absorption in the NIR-II window.
Compared with lipid, blood and water, such SPN shows outstanding PA contrast in
the NIR-II window <i>in situ</i> and <i>in vivo</i>, and an imaging depth of
more than 5 cm at 1064 nm excitation is achieved in chicken-breast tissue.
These results suggest that SPN as a PA contrast in the NIR-II window opens new
opportunities for biomedical imaging with improved imaging contrast and centimeter-deep
imaging depth.</p>
<p>Next, targeted PA
imaging of prostate cancer is achieved by functionalizing a NIR-II absorbing SPN
with prostate-specific membrane antigen (PSMA)-targeted ligands. Insights
into the interaction of the imaging probes with the biological targets are
obtained from single-cell to whole-organ by transient absorption (TA)
microscopy and PA imaging. TA microscopy reveals the targeting efficiency,
kinetics, and specificity of the functionalized SPN to PSMA-positive prostate
cancer at cellular level. Meanwhile, the functionalized SPN demonstrates
selective accumulation and retention in the PSMA-positive tumor after intravenous
administration <i>in vivo</i>. Taken together, it is demonstrated that BTII-DUPA
SPN is a promising targeted probe for prostate cancer diagnosis by PA imaging. </p>
<p>Lastly,
PA imaging in the NIR-II window is also achieved water-soluble semiconducting
polymer, which is prepared by oxygen-doping. After doping, it shows broadband
absorption in the entire NIR-II window, with great chemical stability,
photostability and biocompatibility. Owing to its merit of broadband
absorption, the imaging depth comparison among different NIR-II wavelengths is also
achieved. Moreover, this doped semiconducting polymer is readily soluble in
normal physiological pH by virtue of carboxyl groups on side chains and tends
to aggregate at an acidic environment which results in a 7.6-fold PA
enhancement at pH 5.0. Importantly, a 3.4±1.0-fold greater signal in tumor
tissue than that in muscle is revealed <i>in vivo</i>. This study provides a
more attainable yet effective platform to the field for achieving water-soluble
NIR-II absorbing contrast agents for activatable PA imaging. </p>
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New dopable semiconducting polymer materials enabling novel device architectureTsuda, Takuya 15 October 2021 (has links)
Semiconducting polymers are promising materials for next-generation, flexible electronics devices. Over the last decades, various types of polymers have been developed and applied to devices such as light-emitting diodes (OLEDs), photovoltaics (OPVs), and field-effect transistors (OFETs). Conductivity is one of the most important parameters for the device performance since it directly affects charge carrier collection, injection, and transport. Besides, not only bulk conductivity but also interfacial energy barrier is critical for multilayer devices, especially an energy alignment of layers is essential to collect/inject charge carriers smoothly. Therefore reliable systems for both p- and n-type doping are sought after. Chemical doping (molecular doping) is a promising technique to achieve both, to enhance the conductivity in polymers and to shift energy levels by generating charge carriers (holes or electrons) in polymer films. The method enables to transport charge carriers in thin films or between neighboring layers effectively.
This thesis investigates the chemical doping from the nanostructure level, particularly two types of devices where doping plays a crucial role: 1) pressure sensor based on p-doped semiconducting polymer nanopillars, 2) novel n-type doping system for a technologically advantageous thick interlayer in organic solar cells.
In the first part, an application of nanostructured p-doped polymer was explored in a new type of device. While p-type doping is relatively common, especially for P3HT or PEDOT:PSS, in OPVs or OFETs, the potential of semiconducting polymer material, especially its mechanical flexibility and high electrical conductivity, is not fully utilized in these types of devices. Therefore new electronic device, a pressure sensor, is fabricated based on nanopillar structures made of p-doped P3HT by a templating method. The highly flexible and conductive nanostructure was obtained by combining templating and chemical doping. Through utilizing the buckling behavior of nanopillars, the pressure sensor was constructed and used for the detection of finger movement and touch sensing with a robotic gripper. Besides, the templating process can be tuned by annealing conditions, that enable adjusting the length of nanopillars and thus sensing properties. Finally, the sensing mechanism was investigated by finite element modeling and Euler buckling theory.
In the second part, n-type doping in novel polymers was investigated. Generally, n-type doping has relatively limited reports since the n-doped state of commonly used polymers is readily oxidized by oxygen or water in air. A newly synthesized series of naphthalene diimide (NDI)-based conjugated polyelectrolytes (CPEs) contains cations in side chains, which stabilize the generated charge carriers. The stability of conductivity, spectroscopic characteristics, morphology, and the application of CPEs to interlayers in polymer solar cells (PSCs) were investigated. The polymer film showed air-stable high conductivity by introducing self-compensation doping and anion doping methods. The LUMO level of CPEs has a strong correlation with the conductivity in air and long-term stability. Moreover, the work function of the ITO cathode can be shifted by CPEs and the chemical doping, enabling a highly conductive, thick cathode interlayer, applicable to scalable film deposition methods, e.g., the blade-coating method.
For the outlook, various new applications can be realized by combining these techniques and materials for p-/n-doping systems. This research expands the utilization of semiconducting polymer as a nano-structurable, flexible, highly conductive, and air-stable component for future flexible electronics devices.
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Ultrafast electronic processes at nanoscale organic-inorganic semiconductor interfacesParkinson, Patrick January 2009 (has links)
This thesis is concerned with the influence of nanoscale boundaries and interfaces upon the electronic processes that occur within both organic and inorganic semiconductors. Photoluminescent polymers, highly conducting polymers and nanoscale inorganic semiconductors have been investigated using state-of-the-art ultrafast optical techniques, to provide information on the sub-picosecond photoexcitation dynamics in these systems. The influence of dimensionality on the excitation transfer dynamics in a conjugated polymer blend is studied. Using time-resolved photoluminescence spectroscopy, the transfer transients both for a three-dimensional blend film, and for quasi-two-dimensional monolayers formed through intercalation of the polymer blend between the crystal planes of a SnS2 matrix have been measured. A comparison of the experimental data with a simple, dimensionality-dependent model is presented, based on point dipole electronic coupling between electronic transition moments. Within this approximation, the energy transfer dynamics are found to adopt a three-dimensional character in the solid film, and a two-dimensional nature in the monolayers present in the SnS2 -polymer nanocomposite. The time-resolved conductivity of isolated GaAs nanowires has been investigated by optical-pump terahertz-probe time-domain spectroscopy. The electronic response exhibits a pronounced surface plasmon mode that forms within 300 fs, before decaying within 10 ps as a result of charge trapping at the nanowire surface. The mobility has been extracted using the Drude model for a plasmon and is found to be remarkably high, being roughly one third of that typical for bulk GaAs at room-temperature and indicating the high quality and low bulk defect density in the nanowires studied. Finally, the time-resolved conductivity dynamics of photoexcited polymer-fullerene bulk heterojunction blends for two model polymers, P3HT and MDMO-PPV, blended with PCBM are presented. The observed terahertz-frequency conductivity is characteristic of dispersive charge transport for photoexcitation both at the π−π* absorption peak (560 nm for P3HT), and significantly below it (800 nm). The photoconductivity at 800 nm is unexpectedly high, which is attributed to the presence of a charge transfer complex. In addition, the excitation-fluence dependence of the photoconductivity is studied over more than four orders of magnitude. The time-averaged photoconductivity of the P3HT:PCBM blend is over 20 times larger than that of P3HT, indicating that long-lived positive polarons are responsible for the high photovoltaic efficiency of polymer:fullerene blends. At early times (~ ps) the linear dependence of photoconductivity upon fluence indicates that interfacial charge transfer dominates as an exciton decay pathway, generating charges with mobility of at least ~0.1cm2 V−1 s−1. At later times, a sub-linear relationship shows that carrier-carrier recombination effects influence the conductivity on a longer timescale (> 1 μs).
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Multicomponent assemblies for organic electronics / Assemblage multi-composant pour l'électronique organiqueRekab, Wassima 09 January 2017 (has links)
Mon travail de thèse porte sur l’assemblage supramoléculaire et le transport de charge des multi-composants utilisés dans le domaine de l’électronique à base organique. En particulier, l’étude et l’optimisation des transistors organiques à effet de champ (OFETs), des phototransistors, et des inverseurs organiques. Nous avons démontré que la température de recuit des dispositifs OFETs améliore les performances électriques d’un dérivé de fullerène (ICBA). Ces dispositifs dont les surfaces de SiO2 sont fonctionnalisées par OTS ou HMDS ont montrés des mobilités d’électrons de 0.1cm2V-1s-1, qui est la plus élevée par rapport à la littérature. Aussi, nous avons fabriqué des phototransistors à base de mono- et multifibres de PDIF-CN2 qui ont été optimisés par traitements de surfaces du diélectrique (HMDS ou OTS). Les propriétés optoélectroniques de ces dispositifs ont été comparées à ceux des dispositifs à base des couches minces déposés par spin-coating (éduction centrifuge). Nos dispositifs mono-fibres ont montré des valeurs de mobilité plus élevées (supérieure à 2 cm2V-1s-1) par rapport à ceux des multifibres et couches minces. Une telle efficacité de transport d’électrons est le résultat d’une cristallinité très élevée des fibres, qui permet une collecte efficace des excitons photo-générés qui se traduit par la plus haute sensibilité à la lumière (R) et photosensibilité (P) rapportées pour les phototransistors à base de mono-fibre supérieure à 2 × 103 AW-1, et 5 × 103 AW-1. Enfin, un polymère ambipolaire (DPPT-TT) a été utilisé lors de la fabrication de nouveaux dispositifs multifonctionnels par l’addition des molécules diaryléthènes (DAE_tBu et ou DAE_F), dont les propriétés électriques sont contrôlées par la lumière. Cette approche a permis un contrôle optique de gain en tension des inverseurs organiques, ces dispositifs multi-composants sont caractérisés par des gain en tensions très élevées (jusqu’au 504) comparés à ceux reportés dans la littérature (86). Ces travaux réalisés durant cette thèse offrent de nouvelles perspectives dans le domaine de l’optoélectronique et la conception des mémoires optiques. / This thesis is focused on the investigation of supramolecular assemblies and the charge carriers transport across organic single, bi- and three-component materials, used as the active layer in organic field-effect transistors (OFET), phototransistors (OPT) and complementary inverters. We demonstrated that thermal annealing and duration has high impact in OFET performances based on a fullerene derivative called ICBA. The devices electron mobility enhanced upon HMDS and OTS treated SiO2 surface and reached 0.1 cm2V-1s-1, which is the highest reported value in literature. We have provided evidence for the influence of the order at the supramolecular level in the semiconducting material (PDIF-CN2) on the performance of OPTs. We compared solution processed single crystalline PDIF-CN2 fibers and multifiber assemblies with spin-coated thin films, which revealed that the former exhibited good electron mobility up to 2 cm2s-1V-1. The improved fiber crystallinity allows efficient collection of photogenerated excitons, results in the highest reported responsivity R (>5 × 103 AW-1), and photoswitching ratio P (>2 × 103), which are to date the highest reported in literature for PDI-single crystal OPTs. Finally, we have performed for the first time new multifunctional devices combining an ambipolar polymer (DPPT-TT) with inserted diarylethene molecules in its matrix. The fabricated OFET and organic complementary inverters were optically controlled. The resultant inverters gain values are tuned by ultraviolet and visible light irradiation, reaching 504, which is higher than those reported in literature (86). These findings qualify them as promising potential candidates for the construction of high-performance integrated logic circuits and memory chips.
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Étude de semi-conducteurs par spectroscopie d'excitation cohérente multidimensionnelleGrégoire, Pascal 07 1900 (has links)
No description available.
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Charge Transport in Semiconducting Polymer DevicesAnjaneyulu, Ponnam January 2012 (has links) (PDF)
Understanding the fundamentals of Organic semiconductors is crucial aspect towards the technological applications. Conjugated polymers have shown many interesting physical properties. Especially the electronic and optical properties of these materials have great impact on the daily life. Much work has been devoted to gain the knowledge on the electrical and photo physical properties of these materials. Despite the large number of studies in fabrication and characterisation on these devices some of the fundamental properties like charge transport, carrier generation and its control by doping are not well accomplished.
The Thesis consists of 6 chapters. First chapter is a brief introduction on various properties of semiconducting polymers. Different charge transport models and their basic mechanisms are discussed. Chapter 2 discusses the synthesis, device making and experimental methods used to characterise the polymer devices. Chapter 3 is focused on transport properties in polypyrrole devices and its variation with different experimental conditions. Chapter 4 is aimed to understand the anomalies in the current-voltage characteristics appearing in some of the thiophene based devices. In Chapter 5, the impedance measurement technique is used to characterise the poly (3-hexylthiophene) devices and the outcomes are presented and chapter 6 summarises all the experimental results obtained in this thesis work and presents some future aspects and directions.
Chapter 1: Some of the basic properties and recent advancements in the field of organic semiconductors are discussed in this chapter. Organic semiconductor devices based on conjugated polymers are now becoming alternatives to inorganic semiconductors in many fields. Mobility of these conjugated polymers can be increased by adding dopants and also by choosing appropriate metal contacts for charge injection and extraction. The complexity of the metal-polymer interfaces can be better understood by varying the carrier density and studying their transport properties with various experimental tools.
Chapter 2: The polymer films prepared in this study are electrochemically deposited on to various conducting substrates. The doping and de-doping of the carriers is done by passing a current and reversing its polarity for different time intervals. Device structures for the measurements are obtained by making a top contact on top of the polymer layer. The current-voltage (I-V) and impedance measurements are carried out in metal-polymer-metal geometry. Temperature dependent studies down to 10 K were performed in a continuous flow cryostat to understand the role of temperature in transport studies. Impedance and light measurements are also carried out in the same geometry.
Chapter 3: Transport measurements on polypyrrole devices have shown a space-charge limited (SCLC) conduction, which is also known as bulk property of the materials. I-V curves displayed non-ohmic behaviour at higher voltages and by varying the carrier density the devices show a transition from trap controlled SCLC to trap free/trap filled SCLC. Traps distribution and energies are estimated from the temperature dependent I-V measurements. Poole-Frenkel behaviour, i.e. field dependent mobility is observed in all the polypyrrole samples. The zero field mobility follows Arrhenius behaviour at higher temperatures. Also the temperature variation of mobility displays field dependent and field independent regimes in fully doped and lightly de-doped polypyrrole films. A zero-bias anomaly is observed as the field goes to zero value below 50 K, due to coulomb-blockade transport. Capacitance measurements have shown pseudo inductive behaviour at higher bias, which is also connected with trap-filling regime of PPy devices.
Chapter 4: Current-Voltage anomalies are observed in polythiophene (PTh) and poly (3-methylthiophene) [P3MeT] based devices. The origin of this anomaly is not straight forward in polymer devices, so we investigated it in detail. We propose this is a property specific to the above two materials from various experimental studies. The anomalous behaviour appears when the bias is swept from negative to positive keeping the substrate deposited with polymer as anode. The magnitude of peak to valley current ratio (PVCR) which characterises the merit of device can be varied more than two orders of magnitude by varying the carrier density and as well as by varying scan rate. Since the trap states are also one of the reasons for the origin of this anomaly the rate of filling of these states can be helpful in tuning the magnitude of PVCR. Photo generated carriers in the above devices also help in tuning and controlling the magnitude of anomaly, which can make this device as a suitable candidate for opto-electronic studies. Different conductive substrates such as indium tin oxide, platinum, gold and stainless steel are used for deposition of the above polymers. Top contacts (gold, silver and aluminium) have been also varied to understand the origin of this anomaly. Anomalies are observed with all these different substrates and different top contacts. Finally impedance measurements have shown an elongated tail in the Cole-Cole plot in the region of NDR.
Chapter 5: Impedance measurements on poly (3-hexylthiophene) devices have shown different relaxation mechanism by varying the doping concentration. For moderately doped devices the relaxation mechanism is classical Debye-type, whereas for highly de-doped samples the relaxation time of the carriers is distributed. Charge transport parameters such as contact resistance, mobility and conduction mechanism details can be obtained by identifying and fitting the data to the equivalent circuit model. The relaxation time of the carriers can give rough estimation of mobility and capacitance. The capacitance variation with applied bias gives the nature of conduction mechanism in the devices. If the capacitance variation is unaffected by the applied bias the transport is bulk limited, if it changes significantly the transport can be considered as either contact limited or depletion layer controlled. Current-Voltage measurements also show that Schottky behaviour is present in all the devices. The rectification ratio varies with doping concentration; at one optimum
doping concentration the rectification is very high. I-V measurements on P3MeT devices with varying carrier density have shown a transition in the conduction mechanism from SCLC to contact limited. In the devices with less carrier density the contact limited mechanism is dominating at lower bias voltage and as the bias increases the bulk limited transport takes over. This highlights the role of carrier density in the transport mechanism.
Chapter 6: The conclusions from all the works presented in the thesis are summarised in this chapter. Some of the future directions works are presented.
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Conformation And Charge Transpsort In Conducting Polymers, Carbon Nanotubes And Their NanocompositesChoudhury, Paramita Kar 05 1900 (has links) (PDF)
The main motivation in this thesis is to compare the conformation and charge transport in conducting polymers and carbon nanotubes (CNTs) and to investigate those physical properties in their combined form of nanocomposites. It is known that both conducting polymers and carbon nanotubes are intrinsically 1-dimensional systems which consist of delocalized π-electrons. However, the main difference between these is the fact that flexibility of conducting polymers can be varied depending on the extent of conjugation while CNTs are rigid. Hence a comparison of electronic properties as correlated to their morphology has been carried out and their individual role in nanocomposites is further studied.
The thesis consists of 6 chapters and appendix. Chapter 1 consists of brief introduction of general properties of both conducting polymers, CNTs and their nanocomposites. Chapter 2 deals with the sample preparation and experimental techniques used for the work. Chapter 3 elaborates on the conformational / structural studies on the systems. Chapter 4 focuses on the transport measurements to study the electronic properties of the samples. Chapter 5 reveals the magnetic properties of these systems which can be applied in technological devices. And chapter 6 gives the conclusion and future directions of the work being done.
Chapter 1: Nanocomposites represent a guest-host matrix consisting of easily processible functionalized conjugated polymer as host, incorporating carbon nanotubes as fillers with versatile electronic and magnetic properties, which provide a wide range of technological applications. The conformation, charge dynamics as well as magnetic properties of these conducting polymers and carbon nanotubes, and various aspects of transport mechanism and spin dynamics present in the nanocomposite matrix are studied and presented in a consistent framework.
Chapter 2: The multiwall carbon nanotubes (MWNTs) are grown by thermal chemical vapor deposition (CVD). The MWNTs are dispersed in solution of conducting polymers by ultrasonication and then the suspension is cast on glass substrate and slowly dried by moderate heating. Once dried completely, the free-standing films of thickness 15-25 μm are peeled off the substrate for measurements. The MWNTs, above a certain concentration, form an interconnected network in the 3-dimensional polymer matrix, following percolation mechanism. The disorder is brought into the system mainly by bundling of tubes and bundle intersections. The morphology and conformation of the samples are studied by SEM, TEM and small angle X-ray scattering (SAXS) techniques.
Chapter 3: Small angle X-ray scattering (SAXS) studies in polymeric systems are carried out to probe local nanoscale morphology at various length scales to show the correlation among conformation and assembly of chains.
Small angle X-ray scattering (SAXS) studies are carried out in poly [2-methoxy5-(2’–ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution of varying conjugation lengths as well as different solvents. By increasing the extent of πconjugation from 30 to 100 %, the persistence length increases by a factor of three. Moreover, a pronounced second peak in the pair distribution function is observed in fully conjugated chain, at larger length scales which indicates that the chain segments tend to self-assemble as the conjugation along the chain increases.
The chain assembly and aggregation are further studied for suspensions of MWNTs in polyethylene dioxythiophene-polystyrene (PEDOT-PSS) with aqueous medium and DMSO (dimethyl sulphoxide). The SAXS profile of MWNT dispersion in aqueous PEDOT-PSS clearly show rigid-rod feature of the individual nanotubes evident by the q-1 behavior at short ranges. The crossover from q-1 to q-2 in the longer range further suggest that the suspension consists of individual nanotubes, nanotubes bundles and aggregates that give rise to a 3-dimensonal meshwork of intersecting tubes and ropes. For the MWNT dispersion in PEDOT-PSS with DMSO, however, such q-1 behavior is absent; which evidently shows that the rods are not isolated in the solution and are rather agglomerated. How these conformations affect the electrical and magnetic properties of these systems are studied further in Chapter 4.
Chapter 4: Transport mechanism in single wall carbon nanotubes (SWNT), MWNT
pellets, and nanocomposite films of MWNT and PEDOT-PSS is studied.
The positive and negative magnetoresistance (MR) data in various SWNT samples are analyzed by taking into account the electron-electron interaction (EEI) contribution, in addition to the weak localization (WL) regime. The contribution from EEI to the total MR is confirmed from the universal scaling of MC relation showing that EEI plays a significant role at higher fields and lower temperatures. Intrinsic parameters like inelastic scattering length extracted for barely metallic sample follows the T-3/4 dependence due to inelastic electron-electron scattering in the dirty limit.
Conductivity and magnetoresistance (MR) measurements on nanocomposite films with varying MWNT content (0.03 - 3 %) are performed at a field range 0-11 Tesla, and temperature range 1.3–300 K. The temperature dependence of resistance above 4 K suggests a Coulomb-gap variable range hopping (CG-VRH) transport in the network. Alhough solely negative MR (~ 5-6 %) is observed for pristine MWNT pellets; the nanocomposite films show a combination of large negative MR (~ 80 %) at T < 4 K, and a comparatively weaker positive MR (~ 30 %) for T > 4 K. This suggest that there are two mechanism interplaying and dominant at different temperature regimes which can be explained by the mechanism of transport of the charge carriers of MWNT intervened by that of the polymer matrix.
In conclusion how the individual properties of conducting polymer and carbon
nanotubes contribute to the unique electronic and conformational properties in their
nanocomposites is framed in this investigation.
Chapter 5: Magnetic properties of the pristine MWNTs as well as metal nanowires of nickel, nickel-iron (NiFe), nickel-iron-cobalt (NiFeCo) encapsulated in the MWNTs are studied using superconducting quantum interference device (SQUID) magnetometer.
A typical example of Ni nanowires encapsulated in MWNT (Ni-MWNT) is taken and the results are compared to other forms of nickel (bulk, nanorod cluster, nanowire) to see the effect of size, shape and environment on the magnetic kproperties. The saturation magnetization and coercivity for Ni-MWNTs are 1.0 emu/gm and 230 Oe.
The temperature dependence of magnetization indicates superparamagnetic which is supported by the field-cooled and zero-field-cooled plots determining a blocking temperature ~ 300 K. These altered magnetic properties of Ni-MWNTs are mainly due to the contribution from carbon nanotube encapsulation.
Both the shape and environment enhance the total magnetic anisotropy of encapsulated nanowires at least by a factor of four.
The encapsulation of metal nanowires in MWNTs tunes the magnetic properties of the system widely, e.g. from diamagnetic (pristine MWNTs) to paramagnetic (Ni-MWNT) to ferromagnetic (NiFe-MWNT) and a combination of para and ferro (NiFeCo-MWNT).
Chapter 6: The conclusions of the different works presented in the thesis are coherently summarized in this chapter. Thoughts for future directions are also summed up.
Appendix A: Spin dynamics in conducting polymer PEDOT-PSS in its pristine, processed with DMSO and nanocomposite form (with carbon nanotubes) is studied using solid state nuclear magnetic resonance (NMR). Plots of proton spin lattice relaxation times vs. temperature at a fixed frequency 23.4 MHz are compared to study the effect of the external agents on the polymer dynamics.
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