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(1 - 9 of 9)
- Title
- Optical and Magnetic properties of nanostructures.
- Creator
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Nayyar, Neha, Rahman, Talat, Stolbov, Sergey, Ishigami, Marsahir, Hernandez, Florencio, University of Central Florida
- Abstract / Description
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In this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms...
Show moreIn this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms in the chain is larger than 5. The plasmon energy decreases with further with increasing number of atoms (N) and is almost N-independent when N is larger than 20. In the case of coupled pure chains it was found that the plasmon energy grows as square root of the number of chains, and reaches the visible light energy 1.8eV for the case of three parallel chains. Doping of pure Au chains with transition-metal atoms leads in many cases to formation of additional plasmon peaks close in energy to the undoped chain peak. This peak comes from the local charge oscillations around the potential minima created by the impurity atom. The effect is especially pronounced for Ni-doped chains. In the multiple-chain case, we find an unusual hybridization of the two different (local and collective) plasmon modes. Changing the chain size and chemical composition in the array can be used to tune the absorption properties of nanochains. The case of coupled finite (plasmonic) and infinite (semiconductor, excitonic) chains was also analyzed. We find that one can get significant exciton-plasmon coupling, including hybridized modes and energy transfer between these excitations, in the case of doped chains. The impurity atoms are found to work as attraction centers for excitons. This can be used to transform the exciton energy into local plasmon oscillations with consequent emission at desired point (at which the impurity is located). In a related study the optical properties of single layer MoS2 was analyzed with a focus on the possibility of ultrafast emission, In particular, it was found that the system can emit in femto-second regime under ultrafast laser pulse excitations. Finally, we have studied the magnetic properties of FeRh nanostructures to probe whether there is an antiferromagnetic to ferromagnetic transition as a function of the ratio of Fe and Rh atoms, as in the bulk alloy.. Surprisingly, the ferromagnetic phase is found to be much more stable for these nanostructures as compared to the bulk, which suggests that band-type effects may be responsible for this transition in the bulk, i.e. the transition cannot be described in terms of modification of the Heisenberg model parameters.
Show less - Date Issued
- 2014
- Identifier
- CFE0005221, ucf:50650
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005221
- Title
- Electronic, Optical, and Magnetic Properties of Graphene and Single-Layer Transition Metal Dichalcogenides in the Presence of Defects.
- Creator
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Khan, Mahtab, Leuenberger, Michael, Mucciolo, Eduardo, Saha, Haripada, Tetard, Laurene, Schoenfeld, Winston, University of Central Florida
- Abstract / Description
-
Two-dimensional (2D) materials, such as graphene and single-layer (SL) transition metal dichalcogenides (TMDCs), have attracted a lot of attention due to their fascinating electronic and optical properties. Graphene was the first 2D material that has successfully been exfoliated from bulk graphite in 2004. In graphene, charge carriers interacting with the honeycomb lattice of carbonatoms of graphene to appear as massless Dirac fermions. Massless quasiparticles with linear dispersion are also...
Show moreTwo-dimensional (2D) materials, such as graphene and single-layer (SL) transition metal dichalcogenides (TMDCs), have attracted a lot of attention due to their fascinating electronic and optical properties. Graphene was the first 2D material that has successfully been exfoliated from bulk graphite in 2004. In graphene, charge carriers interacting with the honeycomb lattice of carbonatoms of graphene to appear as massless Dirac fermions. Massless quasiparticles with linear dispersion are also observed in surface states of 3D topological insulators and quantum Hall edgestates. My first project deals with the two-dimensional Hong-Ou-Mandel (HOM) type interferenceexperiment for massless Dirac fermions in graphene and 3D topological insulators. Since masslessDirac fermions exhibit linear dispersion, similar to photons in vacuum, they can be used to observethe HOM interference intensity pattern as a function of the delay time between two massless Dirac fermions. My further projects and the major part of this dissertation deal with single-layer (SL) transition metal dichalcogenides (TMDCs), such as MoS$_2$, WS$_2$, MoSe$_2$ and WSe$_2$, which have recently emerged as a new family of two-dimensional (2D) materials with great interest, not only from the fundamental point of view, but also because of their potential application to ultrathin electronic and optoelectronic devices. In contrast to graphene, SL TMDCs are direct band semiconductors and exhibit large intrinsic spin-orbit coupling (SOC), originating from the d orbitals of transition metal atoms. Wafer-scale production of SL TMDCs is required for industrial applications. It has been shown that artificially grown samples of SL TMDCs through various experimental techniques, such as physical vapor deposition (PVD), chemical vapor deposition (CVD), and molecular beam epitaxy (MBE), are not perfect, instead certain type of imperfections such as point defects are always found to be present in the grown samples. Defects compromise the crystallinity of the sample, which results in reduced carrier mobility and deteriorated optical efficiency. However, defects are not always unwanted; in fact, defects can play an important role in tailoring electronic, optical, and magnetic properties of materials. Using Density functional theory we investigate the impact of point defects on the electronic, optical, and magnetic properties of SL TMDCs. First, we show that certain vacancy defects lead to localized defect states, which in turn give rise to sharp transitions in in-plane and out-of-plane optical susceptibilities of SL TMDCs. Secondly, we show that a naturally occurring antisite defect Mo$_S$ in PVD grown MoS$_2$ is magnetic in nature with a magneticmoment of 2$\mu_B$, and remarkably exhibit an exceptionally large atomic scale magnetic anisotropy energy (MAE) of ~ 500 eV. Both magnetic moment and MAE can be tuned by shifting the position of the Fermi level which can be achieved either by gate voltage or by chemical doping. Thirdly, we argue that the antisite defect Se$_W$ in WSe$_2$ leads to long lived localized excited states, which can explain the observed single quantum emitters in CVD grown WSe$_2$ samples, with potential application to quantum cryptography.
Show less - Date Issued
- 2018
- Identifier
- CFE0007030, ucf:52047
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007030
- Title
- CHEMICAL STRUCTURE - NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF TWO-PHOTON ABSORBING FLUORENE MOLECULES.
- Creator
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Hales, Joel McCajah, Van Stryland, Eric W., University of Central Florida
- Abstract / Description
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This dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident...
Show moreThis dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident irradiance and the improved penetration into absorbing media that it affords. As a consequence of the burgeoning field which exploits 2PA, it is a goal to find materials that exhibit strong two-photon absorbing capabilities. Organic materials are promising candidates for 2PA applications because their material properties can be tailored through molecular engineering thereby facilitating optimization of their nonlinear optical properties. Fluorene derivatives are particularly interesting since they possess high photochemical stability for organic molecules and are generally strongly fluorescent. By systematically altering the structural properties in a series of fluorenyl molecules, we have determined how these changes affect their two-photon absorbing capabilities. This was accomplished through characterization of both the strength and location of their 2PA spectra. In order to ensure the validity of these results, three separate nonlinear characterization techniques were employed: two-photon fluorescence spectroscopy, white-light continuum pump-probe spectroscopy, and the Z-scan technique. In addition, full linear spectroscopic characterization was performed on these molecules along with supplementary quantum chemical calculations to obtain certain molecular properties that might impact the nonlinearity. Different designs in chemical architecture allowed investigation of the effects of symmetry, solvism, donor-acceptor strengths, conjugation length, and multi-branched geometries on the two-photon absorbing properties of these molecules. In addition, the means to enhance 2PA via intermediate state resonances was investigated. To provide plausible explanations for the experimentally observed trends, a conceptually simple three level model was employed. The subsequent correlations found between chemical structure and the linear and nonlinear optical properties of these molecules provided definitive conclusions on how to properly optimize their two-photon absorbing capabilities. The resulting large nonlinearities found in these molecules have already shown promise in a variety of the aforementioned applications.
Show less - Date Issued
- 2004
- Identifier
- CFE0000005, ucf:46103
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0000005
- Title
- Growth and doping of MoS2 thin films for electronic and optoelectronic applications.
- Creator
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Abouelkhair, Hussain, Peale, Robert, Kaden, William, Stolbov, Sergey, Coffey, Kevin, University of Central Florida
- Abstract / Description
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MoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning...
Show moreMoS2 high absorption coefficient, high mobility, mechanical flexibility, and chemical inertness is very promising for many electronic and optoelectronic applications. The growth of high-quality MoS2 by a scalable and doping compatible method is still lacking. Therefore, the suitable dopants for MoS2 are not fully explored yet. This dissertation consists mainly of four main studies. The first study is on the growth of MoS2 thin films by atmospheric pressure chemical vapor deposition. Scanning electron microscope images revealed the growth of microdomes of MoS2 on top of a smooth MoS2 film. These microdomes are very promising as a broadband omnidirectional light trap for light harvesting applications. The second study is on the growth of MoS2 thin films by low pressure chemical vapor deposition (LPCVD). Control of sulfur vapor flow is essential for the growth of a pure phase of MoS2. Turning off sulfur vapor flow during the cooling cycle at 700 (&)#186;C leads to the growth of highly textured MoS2 with a Hall mobility of 20 cm2/Vs. The third study was on the growth of Ti-doped MoS2 thin films by LPCVD. The successful doping was confirmed by Hall effect measurement and secondary ion mass spectrometry (SIMS). Different growth temperatures from 1000 to 700 ? were studied. Ti act as a donor in MoS2. The fourth study is on fluorine-doped SnO2 (FTO) which has many technological applications including solar cells and transistors. FTO was grown by an aqueous-spray-based method. The main objective was to compare the actual against the nominal concentration of fluorine using SIMS. The concentration of fluorine in the grown films is lower than the concentration of fluorine in the aqueous solution.?
Show less - Date Issued
- 2017
- Identifier
- CFE0006847, ucf:51767
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0006847
- Title
- INVESTIGATION OF REACTIVELY SPUTTERED BORON CARBON NITRIDE THIN FILMS.
- Creator
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Todi, Vinit, Sundaram, Kalpathy, University of Central Florida
- Abstract / Description
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Research efforts have been focused in the development of hard and wear resistant coatings over the last few decades. These protective coatings find applications in the industry such as cutting tools, automobile and machine part etc. Various ceramic thin films like TiN, TiAlN, TiC, SiC and diamond-like carbon (DLC) are examples of the films used in above applications. However, increasing technological and industrial demands request thin films with more complicated and advanced properties. For...
Show moreResearch efforts have been focused in the development of hard and wear resistant coatings over the last few decades. These protective coatings find applications in the industry such as cutting tools, automobile and machine part etc. Various ceramic thin films like TiN, TiAlN, TiC, SiC and diamond-like carbon (DLC) are examples of the films used in above applications. However, increasing technological and industrial demands request thin films with more complicated and advanced properties. For this purpose, B-C-N ternary system which is based on carbon, boron and nitrogen which exhibit exceptional properties and attract much attention from mechanical, optical and electronic perspectives. Also, boron carbonitride (BCN) thin films contains interesting phases such as diamond, cubic BN (c-BN), hexagonal boron nitride (h-BN), B4C, [two]-C3N4. Attempts have been made to form a material with semiconducting properties between the semi metallic graphite and the insulating h-BN, or to combine the cubic phases of diamond and c-BN (BC2N heterodiamond) in order to merge the higher hardness of the diamond with the advantages of c-BN, in particular with its better chemical resistance to iron and oxygen at elevated temperatures. New microprocessor CMOS technologies require interlayer dielectric materials with lower dielectric constant than those used in current technologies to meet RC delay goals and to minimize cross-talk. Silicon oxide or fluorinated silicon oxide (SiOF) materials having dielectric constant in the range of 3.6 to 4 have been used for many technology nodes. In order to meet the aggressive RC delay goals, new technologies require dielectric materials with K<3. BCN shows promise as a low dielectric constant material with good mechanical strength suitable to be used in newer CMOS technologies. For optical applications, the deposition of BCN coatings on polymers is a promising method for protecting the polymer surface against wear and scratching. BCN films have high optical transparency and thus can be used as mask substrates for X-ray lithography. Most of the efforts from different researchers were focused to deposit cubic boron nitride and boron carbide films. Several methods of preparing boron carbon nitride films have been reported, such as chemical vapor deposition (CVD), plasma assisted CVD, pulsed laser ablation and ion beam deposition. Very limited studies could be found focusing on the effect of nitrogen incorporation into boron carbide structure by sputtering. In this work, the deposition and characterization of amorphous thin films of boron carbon nitride (BCN) is reported. The BCN thin films were deposited by radio frequency (rf) magnetron sputtering system. The BCN films were deposited by sputtering from a high purity B4C target with the incorporation of nitrogen gas in the sputtering ambient. Films of different compositions were deposited by varying the ratios of argon and nitrogen gas in the sputtering ambient. Investigation of the oxidation kinetics of these materials was performed to study high temperature compatibility of the material. Surface characterization of the deposited films was performed using X-ray photoelectron spectroscopy and optical profilometry. Studies reveal that the chemical state of the films is highly sensitive to nitrogen flow ratios during sputtering. Surface analysis shows that smooth and uniform BCN films can be produced using this technique. Carbon and nitrogen content in the films seem to be sensitive to annealing temperatures. However depth profile studies reveal certain stoichiometric compositions to be stable after high temperature anneal up to 700[degrees]C. Electrical and optical characteristics are also investigated with interesting results. The optical band gap of the films ranged from 2.0 eV - 3.1 eV and increased with N2/Ar gas flow ratio except at the highest ratio. The optical band gap showed an increasing trend when annealed at higher temperatures. The effect of deposition temperature on the optical and chemical compositions of the BCN films was also studied. The band gap increased with the deposition temperature and the films deposited at 500oC had the highest band gap. Dielectric constant was calculated from the Capacitance-Voltage curves obtained for the MOS structures with BCN as the insulating material. Aluminum was used as the top electrode and the substrate was p-type Si. Effect of N2/Ar gas flow ratio and annealing on the values of dielectric constant was studied and the dielectric constant of 2.5 was obtained for the annealed BCN films. This by far is the lowest value of dielectric constant reported for BCN film deposited by sputtering. Lastly, the future research work on the BCN films that will be carried out as a part of the dissertation is proposed.
Show less - Date Issued
- 2011
- Identifier
- CFE0004033, ucf:49181
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0004033
- Title
- Tuning chemical and optical properties of nanomaterials: From extended surfaces to finite nanoclusters.
- Creator
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Hooshmand Gharehbagh, Zahra, Rahman, Talat, Kara, Abdelkader, Kaden, William, Uribe Romo, Fernando, University of Central Florida
- Abstract / Description
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Modifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233;...
Show moreModifying the electronic and optical properties of surfaces and nanostructures are in the forefront of surface science. This dissertation's focus is on this problem. The first part is on the adsorption of functionalized naphthalene molecules on Cu(111) surface. The results show that changing the functional group results in modification of charge redistribution at the interface of molecule and surface and the electronic structure of Cu changes. The second part discusses the new Moir(&)#233; structure of h-BN on Rh(111) induced by intrinsic carbon impurities of Rh single crystals. We found that these impurities intercalate between h-BN and Rh(111) with new local properties such as charge transfer from Rh and C atoms to h-BN such as appearance of new states in the BN. The third part is about the study of CO super lattice structure at 1/2ML when adsorbed on Pd(111). By considering all the possible overlayer structures and using several different functionals, we found that two structures can be made by CO adsorbents and all the other structures convert to one of these two. The fourth part is on the electronic and optical properties of ligated Ag44 nanoclusters. Using DFT and TDDFT calculations we show that when the pH level of a solvent is changed, the protecting ligands deprotonate and their interaction with each other as well as the metal core varies and the new peaks in absorption spectrum arise from electron rich deprotonated ligands. The final part is on the adsorption of planar molecules on MoS2. We found that the isomers of di-iodobenzene adsorb with same strength on MoS2 and it is the symmetry of frontier orbitals that identifies their different behavior. Also the adsorption and dissociation of benzenethiol on MoS2 was studied and the results show that benzenethiol dissociates only in the presence of defects and heals the structure.
Show less - Date Issued
- 2018
- Identifier
- CFE0007337, ucf:52138
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007337
- Title
- NONLINEAR OPTICAL PROPERTIES OF ORGANIC CHROMOPHORES CALCULATED WITHIN TIME DEPENDENT DENSITY FUNCTIONAL THEORY.
- Creator
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Tafur, Sergio, Kokoouline, Viatcheslav, University of Central Florida
- Abstract / Description
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Time Dependent Density Functional Theory offers a good accuracy/computational cost ratio among different methods used to predict the electronic structure for molecules of practical interest. The Coupled Electronic Oscillator (CEO) formalism was recently shown to accurately predict Nonlinear Optical (NLO) properties of organic chromophores when combined with Time Dependent Density Functional Theory. Unfortunately, CEO does not lend itself easily to interpretation of the structure activity...
Show moreTime Dependent Density Functional Theory offers a good accuracy/computational cost ratio among different methods used to predict the electronic structure for molecules of practical interest. The Coupled Electronic Oscillator (CEO) formalism was recently shown to accurately predict Nonlinear Optical (NLO) properties of organic chromophores when combined with Time Dependent Density Functional Theory. Unfortunately, CEO does not lend itself easily to interpretation of the structure activity relationships of chromophores. On the other hand, the Sum Over States formalism in combination with semiempirical wavefunction methods has been used in the past for the design of simplified essential states models. These models can be applied to optimization of NLO properties of interest for applications. Unfortunately, TD-DFT can not be combined directly with SOS because state-to-state transition dipoles are not defined in the linear response TD approach. In this work, a second order CEO approach to TD-DFT is simplified so that properties of double excited states and state-to-state transition dipoles may be expressed through the combination of linear response properties. This approach is termed the a posteriori Tamm-Dancoff approximation (ATDA), and validated against high-level wavefunction theory methods. Sum over States (SOS) and related Two-Photon Transition Matrix formalism are then used to predict Two-Photon Absorption (2PA) profiles and anisotropy, as well as Second Harmonic Generation (SHG) properties. Numerical results for several conjugated molecules are in excellent agreement with CEO and finite field calculations, and reproduce experimental measurements well.
Show less - Date Issued
- 2007
- Identifier
- CFE0001853, ucf:47372
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0001853
- Title
- Optical Properties of Single Nanoparticles and Two-dimensional Arrays of Plasmonic Nanostructures.
- Creator
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Zhou, Yadong, Zou, Shengli, Harper, James, Zhai, Lei, Chen, Gang, Zheng, Qipeng, University of Central Florida
- Abstract / Description
-
The tunability of plasmonic properties of nanomaterials makes them promising in many applications such as molecular detection, spectroscopy techniques, solar energy materials, etc. In the thesis, we mainly focus on the interaction between light with single nanoparticles and two-dimensional plasmonic nanostructures using electrodynamic methods. The fundamental equations of electromagnetic theory: Maxwell's equations are revisited to solve the problems of light-matter interaction, particularly...
Show moreThe tunability of plasmonic properties of nanomaterials makes them promising in many applications such as molecular detection, spectroscopy techniques, solar energy materials, etc. In the thesis, we mainly focus on the interaction between light with single nanoparticles and two-dimensional plasmonic nanostructures using electrodynamic methods. The fundamental equations of electromagnetic theory: Maxwell's equations are revisited to solve the problems of light-matter interaction, particularly the interaction of light and noble nanomaterials, such as gold and silver. In Chapter 1, Stokes parameters that describe the polarization states of electromagnetic wave are presented. The scattering and absorption of a particle with an arbitrary shape are discussed. In Chapter 2, several computational methods for solving the optical response of nanomaterials when they are illuminated by incident light are studied, which include the Discrete Dipole Approximation (DDA) method, the coupled dipole (CD) method, etc. In Chapter 3, the failure and reexamination of the relation between the Raman enhancement factor and local enhanced electric field intensity is investigated by placing a molecular dipole in the vicinity of a silver rod. Using a silver rod and a molecular dipole, we demonstrate that the relation generated using a spherical nanoparticle cannot simply be applied to systems with particles of different shapes. In Chapter 4, a silver film with switchable total transmission/reflection is discussed. The film is composed of two-dimensional rectangular prisms. The factors affecting the transmission (reflection) as well as the mechanisms leading to the phenomena are studied. Later, in Chapter 5 and 6, the sandwiched nano-film composed of two 2D rectangular prisms arrays and two glass substrates with a continuous film in between is examined to enhance the transmission of the continuous silver film.
Show less - Date Issued
- 2018
- Identifier
- CFE0007117, ucf:51943
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0007117
- Title
- Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations.
- Creator
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Nayyar, Iffat, Masunov, Artem, Saha, Haripada, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
- Abstract / Description
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Organic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged ...
Show moreOrganic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structure-activity relationships useful for technological innovations.In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchange-correlation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations.In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1†) excitons, positive (P+) and negative (P-) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particle-hole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium.In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P+ and P- is determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1†) mostly follows their lattice distortions. Geometry relaxation plays an important role in the localization of the S1 and T1† excitons owing to the non-variational construction of the excited state wavefunction. While, mean-field calculated P+, P- and T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and P- formation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LC-wPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure.In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P+ and P- excitations in PPV and MEH-PPV. We observe that the extent of self-trapping for P+ and P- polarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.
Show less - Date Issued
- 2013
- Identifier
- CFE0005110, ucf:50722
- Format
- Document (PDF)
- PURL
- http://purl.flvc.org/ucf/fd/CFE0005110
