Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.Understanding the interrelations between microstructure and electronic processes in polymeric semiconductors is of great importance for their use in bulk heterostructures, as the active part of power-converting devices such as organic photovoltaic cells or light emitting diodes, as well as for quantum optoelectronics applications. In this doctoral thesis, two different systems are investigated; each of these systems represents a different approach to optimize materials in terms of microstructure and their ability to order on the molecular level. In the first system, by means of quasi-steady-state photoinduced absorption (PIA) and pump-modulation-frequency-dependent PIA spectroscopy, I performed a comprehensive analysis of the working principles of a hybrid photovoltaic cell based on nanocrystals of zinc oxide (ZnO) and poly(3-hexylthiophene) (P3HT). The interface surface area between donor (polymer P3HT) and acceptor (ZnO nanocrystals), where charge generation occurs, plays a significant role in the performance of the hybrid photovoltaic cells. To improve the charge generation mechanism of P3HT: ZnO, it is therefore essential to modify the P3HT: ZnO interface area. We demonstrated that molecular interface modification with cis-bis(4,40-dicarboxy-2,20bipyridine) ruthenium (II) (N3-dye) and a-Sexithiophen-2-yl-phosphonic Acid (6TP) as interface modifiers enhanced the photocurrent and performance in P3HT: ZnO cells. 6TP and N3 attach to the ZnO interface, thus increasing the donor:acceptor interface area that contributes to enhanced charge separation. Furthermore, 6TP and N3 reduce the ZnO traps that reduces recombination. In the second part, I introduced a processed solid-like ultra-high-molecular-weight polystyrene polymeric host matrix to trap and protect poly [2-methoxy, 5-(2’-ethylhexoxy)- 1,4-phenylene vinylene-PPV] (MEH-PPV) solution for use in quantum optoelectronic devices. Previous work by others has shown that MEH-PPV in solution undergoes a conformation transition from coiled conformation at high temperatures (blue-phase) to a chain-extended conformation at low temperatures (red-phase). The chain-extended conformation of MEH-PPV solution favours the characteristics needed to improve quantum optoelectronic devices, however the solution cannot be incorporated into the device. We demonstrated that the red-phase feature of MEH-PPV in solution maintains in a processed solid-like ultra-high-molecular-weight polystyrene polymeric host matrix (MEH-PPV/UHMWPS gels), by means of temperature-dependent photoluminescence (PL) spectroscopy (ranged from 290K down to 80 K). The red-phase of MEH-PPV/UHMW PS gels manifest itself as narrow linewidths and enhanced 0-0 line strength in the PL spectrum as well as a small stokes shifts between the PL and absorption spectra at low temperatures. These approaches demonstrate that microstructure manipulation and electronic properties of polymeric semiconductors have a direct impact on the device performance for their continued technological developments

Energy harvesting using photovoltaic and betavoltaic devices

There is an important need for improvement in both cost and efficiency of photovoltaic cells. For improved efficiency, a better understanding of solar cell performance is required. An analytical model of thin-film silicon solar cell, which can provide an intuitive understanding of the effect of illumination on its charge carriers and electric current, is proposed. The separate cases of homogeneous and inhomogeneous charge carrier generation rates across the device are investigated. This model also provides for the study of the charge carrier transport within the quasi-neutral and depletion regions of the device, which is of an importance for thin-film solar cells. Two boundary conditions, one based on a fixed charge carrier surface recombination velocities at the electrodes and another based on intrinsic conditions for large size devices are explored. The device\u27s short circuit current and open circuit voltage are found to increase with a decrease of surface recombination velocity at the electrodes. The power conversion efficiency of thin film solar cells is observed to depend strongly on impurity doping concentrations. The developed analytical model can be used to optimize the design and performance of thin-film solar cells without involving highly complicated numerical codes to solve the corresponding drift-diffusion equations. The third generation polymer photovoltaic solar cells, the first generation includes monocrystalline silicon solar cells and second generation being thin-film solar cells, and photodetectors are researched widely in the last few years due to their low device processing cost, mechanical flexibility, and lightweight. Organic photovoltaic materials such as poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT: PCBM) blend are usually cheaper than inorganic materials, but have a limitation of lower power conversion efficiency (PCE) than their inorganic (for example, Si) counterparts. These organic devices need to be optimized to achieve the maximum possible PCE. One way to do this is to achieve the optimal thickness of the optically active layer of P3HT:PCBM while fabricating these organic photovoltaic devices. The influence of the active layer\u27s thickness of P3HT:PCBM blend on performance of polymer solar cells and photodetectors are experimentally investigated. The fabricated device structure is glass/ITO/PEDOT:PSS/P3HT:PCBM/A1, where ITO is the indium tin oxide, and PEDOT:PSS stands for poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) used as a buffer layer to collect holes effectively at the ITO anode. Aluminum is used as a cathode. Chlorobenzene is used as a solvent to prepare the polymer-fullerene blend. Spin coating technique was utilized to deposit the active layer and the concentration of P3HT, PCBM, and spin-coating speeds were varied to achieve a wide range of the active layer\u27s thicknesses from 20 mn to 345 mn. The PCE of solar cell devices and the external quantum efficiency ( EQE) of the photodetectors are found to increase with the thickness of the active layer. The maximum PCE of 1.09% is obtained for the active layer\u27s thickness of 345 mn. The ongoing advanced space exploration requires the novel energy sources that can generate power for extreme duration without need of refill. The need for such extreme-duration lightweight power sources for space and terrestrial applications motivates the study and development of polymer-based betavoltaic devices. The betavoltaic devices based on the semiconductive polymer-fullerene blend of P3HT:ICBA, where ICBA is indene-C60 bisadduct, are demonstrated here for the first time. Both direct and indirect energy conversion methods were explored. For the indirect conversion method, a scintillator intermediate layer of cerium-doped yttrium aluminum garnet (Ce:YAG) was used. A high open circuit voltage of 0.56 V has been achieved in the betavoltaic device fabricated on polyethylene terephthalate (PET) substrate with the indirect energy conversion method at 30 keV electron kinetic energy. The directional and external interaction losses are significantly reduced using thin PET substrates. The maximum output electrical power of 62 nW was achieved at 30 keV input electron beam energy. The highest betavoltaic PCE of 0.78% was achieved at 10 keV of electron beam energy. The performance of two different scintillators, Ce:YAG and Thallium doped Cesium Iodide (CsI:TI), were compared in the indirect conversion betavoltaic devices experimentally and the interaction of electron beam with Ce:YAG and CsI:TI was studied using Monte Carlo simulations. The catholuminescence profiles from simulation showed that CsI:TI is more-efficient to generate photons when hit by electron beam compared to Ce:YAG, which is further verified experimentally with 20% PCE enhancement using CsI:TI at 30 kV e-beam compared to betavoltaic devices with Ce:YAG. The directional loss in the indirect conversion devices is further reduced by applying thin reflecting aluminum film on top of the scintillator. The PCE increased by 26.7% with 30 nm thin aluminum film on top of Ce:YAG scintillator at 30 keV electron beam energy. The experimental results showed that the output electrical power from betavoltaic devices increased with the increase in incident electron beam energy

First-Principles Density Functional Theory Study of Novel Materials for Solar Energy Conversion and Environment Applications

To design an efficient solar energy conversion device, theoretical input is extremely important to provide the basic guideline for experimental scientists, to fabricate the most efficient, cheap, and stable device with less efforts. This desire can be made possible if computational scientist use a proper theoretical protocol, design an energy material, then the experimentalist will only invest weeks or months on the synthetic effort. This thesis highlights my recent efforts in this direction. Monoclinic BiVO4 is has been using as a photocatalyst due to its stability, cheap, easily synthesizable, narrow band gap and ideal VB (-6.80 eV vs vacuum) but inappropriate CB (-4.56 eV vs vacuum) edge position, responsible for its low efficiency. We have carried out a comprehensive experimental and periodic density functional theory (DFT) simulations of the pristine, Oxygen defective (Ov), Se doped monoclinic BiVO4 and heterojunction with Selenium (Se-BiVO4), to improve not only its CB edge position but photocatalytic and charge carrier properties. It is found that Ov (1% Oxygen vacancy) and mild doped BiVO4 (1 to 2% Se) are thermodynamically stable, have ideal band edges ~ -4.30 eV), band gaps (~1.96 eV), and small effective masses of electrons and holes. We have also investigated the contribution of Se to higher performance by effecting morphology, light absorption and charge transfer properties in heterojunction. Finally, it is found that Se makes a direct Z-scheme (band alignments) with BiVO4 where the photoexcited electron of BiVO4 recombine with the VB of Se, consequences electron-hole separation at Se and BiVO4, respectively, as a result, enhanced photocurrent is obtained. Theoretical study of β-TaON in the form of primitive unit cell, supercell and its N, Ta, and O terminated surfaces are carried out with the help of periodic DFT. Optical and electronic properties of all these different species are simulated, which predict TaON as the best candidate for photocatalytic water splitting contrast to their Ta2O5 and Ta3N5 counterparts. The calculated bandgap, valence band, and conduction band edge positions predict that β-TaON should be an efficient photoanodic material. The valence band is made up of N 2p orbitals with a minor contribution from O 2p, while the conduction band is made up of Ta 5d. Turning to thin films, the valence band maximum; VBM (−6.4 eV vs. vacuum) and the conduction band minimum; CBM (−3.3 eV vs. vacuum) of (010)-O terminated surface are respectively well below and above the redox potentials of water as required for photocatalysis. Charge carriers have smaller effective masses than in the (001)-N terminated film (VBM −5.8 and CBM −3.7 eV vs. vacuum). However, due to wide band gap (3.0 eV) of (010)-O terminated surface, it cannot absorb visible wavelengths. On the other hand, the (001)-N terminated TaON thin film has a smaller band gap in the visible region (2.1 eV) but the bands are not aligned to the redox potential of water. Possibly a mixed phase material would produce an efficient photoanode for solar water splitting, where one phase performs the oxidation and the other reduction. Computational study of an optically transparent, near-infrared-absorbing low energy gap conjugated polymer, donor−acceptor−donor (D-A-D) with promising attributes for photovoltaic application is reported herein. The D and A moiety on the polymeric backbone have been found to be responsible for tuning the band gap, optical gap, open circuit (Voc) and short-circuit current density (Jsc) in the polymers solar cells (PSC). Reduction in the band gap, high charge transformation, and enhanced visible light absorption in the D-A-D system is because of strong overlapping of molecular orbitals of D and A. In addition, the enhanced planarity and weak steric hindrance between adjacent units of D-A-D, resulted in red-shifting of its onset of absorption. Finally, PSC properties of the designed D-A-D was modeled in the bulk heterojunction solar cell, which gives theoretical Voc of about 1.02 eV. DFT study has been carried out to design a new All-Solid-State dye-sensitized solar cell (SDSC), by applying a donor-acceptor conjugated polymer instead of liquid electrolyte. The typical redox mediator (I1−/I3−) is replaced with a narrow band gap, hole transporting material (HTM). A unique “upstairs” like band energy diagram is created by packing N3 between HTM and TiO2. Our theoretical simulations prove that the proposed configuration will be highly efficient as the HOMO level of HTM is 1.19 eV above the HOMO of sanitizer (dye); providing an efficient pathway for charge transfer. High short-circuit current density and power conversion efficiency is promised from the strong overlapping of molecular orbitals of HTM and sensitizer. A low reorganization energy of 0.21 eV and exciton binding energy of 0.55 eV, confirm the high efficiency of HTM. Theoretical and experimental studies of a series of four porphyrin-furan dyads were designed and synthesized, having anchoring groups, either at meso-phenyl or pyrrole-β position of a zinc porphyrin based on donor–π–acceptor (D–π–A) approach. The porphyrin macrocycle acts as donor, furan hetero cycle acts as π-spacer and either cyanoacetic acid or malonic acid group acts as acceptor. Optical bandgap, natural bonding, and molecular bonding orbital (HOMO–LUMO) analysis confirm the high efficiency pyrrole-β substituted zinc porphyrins contrast to meso-phenyl dyads. DFT study of polypyrrole-TiO2 composites has been carried out to explore their optical, electronic and charge transfer properties for the development of an efficient photocatalyst. Titanium dioxide (Ti16O32) was interacted with a range of pyrrole (Py) oligomers to predict the optimum composition of nPy-TiO2 composite with suitable band structure for efficient photocatalytic properties. The study has revealed that Py-Ti16O32 composites have narrow band gap and better visible light absorption capability compared to individual constituents. A red-shifting in λmax, narrowing band gap, and strong intermolecular interaction energy (-41 to −72 kcal/mol) of nPy-Ti16O32 composites confirm the existence of strong covalent type interactions. Electron−hole transferring phenomena are simulated with natural bonding orbital analysis where Py oligomers found as donor and Ti16O32 as an acceptor in nPy-Ti16O32 composites. Sensitivity and selectivity of polypyrrole (PPy) towards NH3, CO2 and CO have been studied at DFT. PPy oligomers are used both, in the doped (PPy+) and neutral (PPy) form, for their sensing abilities to realize the best state for gas sensing. Interaction energies and amount of charges (NBO and Mulliken charge analysis) are simulated which reveal the sensing ability of PPy towards these gases. PPy, both in doped and neutral state, is more sensitive to NH3 compared to CO2 and CO. More interestingly, NH3 causes doping of PPy and de-doping of PPy+, providing evidence that PPy/PPy+ is an excellent sensor for NH3 gas. UV-vis and UV-vis-near-IR spectra of nPy, nPy+, and nPy/nPy+-X complexes demonstrate strong interaction of PPy/PPy+ with these atmospheric gases. The applications of graphene (GR) and its derivatives in the field of composite materials for solar energy conversion, energy storage, environment purification and biosensor applications have been reviewed. The vast coverage of advancements in environmental applications of GR-based materials for photocatalytic degradation of organic pollutants, gas sensing and removal of heavy metal ions is presented. Additionally, the presences of graphene composites in the bio-sensing field have been also discussed in this review.College Funded University of Exeter, U

Bulk Heterojunction Organic Solar Cells Based on Crosslinked Polymer Donor Networks

Ph.DDOCTOR OF PHILOSOPH

Doctor of Philosophy

dissertationThe temporal dynamics of excitons and the evolution of excited states of a material system reflect both the excitation conditions and the final destination of the excitation energy. Precise control of material structure through modern nanofabrication provides nanostructures with well-defined relaxation paths of excitons, which can be manipulated and probed using external stimulation. In particular, electrostatic manipulation of exciton dynamics with external electric fields can be used to study electronic properties of novel material systems such as semiconductor nanocrystals and pi-conjugated molecules, which may be well suited for future applications in optoelectronic devices. In this work, electric field induced quenching of photoluminescence through generation of indirect excitons is performed on colloidal tetrapod heterostructure nanocrystals and a multichromophoric model molecular system. The dependence of quenching on optical excitation density, which shows opposite trends in these two material systems, reflects the specific origin of quenching in each system. The large reduction in decay lifetime of indirect excitons in the tetrapods also enables storage of optical information with external electric field, which can be observed using time-resolved spectroscopy. As a model light-harvesting system with efficient energy funneling from the arm to the core, the tetrapod is an ideal system to study impact of electric field on multiexcitons in the core and the "hot" excitons in the arm, thus providing insight on the effects of an electric field on intrapartical energy transfer. While energy transfer in the heterostructure tetrapods is through direct charge carrier thermalization, it is the coherent and incoherent energy transfer that couple chromophores in the multichromophoric molecules which mimic the intermolecular interactions in organic electronics. Both single molecule spectroscopy and time-resolved spectroscopy were employed to probe the structural dependent coherent and incoherent energy transfer. Briefly, this work consists of four main results. (1) Quenching in tetrapods is due to the localization of indirect excitons at trap sites which causes saturation of quenching at high excitation density. (2) Multiexcitons and arm excitons with fast decay lifetimes are not affected by an external electric field since electrostatic manipulation is not instantaneous. (3) Coherent coupling between chromophores causes changes in spectrum and decay lifetime, while the incoherent coupling leaves a dimer as a single quantum emitter and causes structural dependent emission depolarization. (4) Field induced quenching increases with the increase of excitation density and number of chromophores in multichorphoric molecules

Characterisation and optimisation of hybrid polymer/metal oxide photovoltaic devices

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