SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS FOR DYE-SENSITIZED SOLAR CELLS

Graphene, which is a two-dimensional carbon material, exhibits unique properties that promise its potential applications in photovoltaic devices. Dye-sensitized solar cell (DSSC) is a representative of the third generation photovoltaic devices. Therefore, it is important to synthesize graphene with special structures, which possess excellent properties for dye-sensitized solar cells. This dissertation research was focused on (1) the effect of oxygen content on the structure of graphite oxide, (2) the stability of graphene oxide solution, (3) the application of graphene precipitate from graphene oxide solution as counter electrode for DSSCs, (4) the development of a novel synthesis method for the three-dimensional graphene with honeycomb-like structure, and (5) the exploration of honeycomb structured graphene (HSG) as counter electrodes for DSSCs. Graphite oxide is a crucial precursor to synthesize graphene sheets via chemical exfoliation method. The relationship between the oxygen content and the structures of graphite oxides was still not explored. In this research, the oxygen content of graphite oxide is tuned by changing the oxidation time and the effect of oxygen content on the structure of graphite oxide was evaluated. It has been found that the saturated ratio of oxygen to carbon is 0.47. The types of functional groups in graphite oxides, which are epoxy, hydroxyl, and carboxylgroups, are independent of oxygen content. However, the interplanar space and BET surface area of graphite oxide linearly increases with increasing O/C ratio. Graphene oxide (GO) can easily dissolve in water to form a stable homogeneous solution, which can be used to fabricate graphene films and graphene based composites. This work is the first research to evaluate the stability of graphene oxide solution. It has been found that the introduction of strong electrolytes (HCl, LiOH, LiCl) into GO solution can cause GO precipitation. This indicates that the electrostatic repulsion plays a critical role in stabilizing aqueous GO solution. Furthermore, the HCl-induced GO precipitation is a feasible approach to deposit GO sheets on a substrate as a Pt-free counter electrode for a dye-sensitized solar cell (DSSC), which exhibited 1.65% of power conversion efficiency. To explore broad and practical applications, large-scale synthesis with controllable integration of individual graphene sheets is essential. A novel strategy for the synthesis of graphene sheets with three-dimensional (3D) Honeycomb-like structure has been invented in this project based on a simple and novel chemical reaction (Li2O and CO to graphene and Li2CO3). The simultaneous formation of Li2CO3 with graphene not only can isolate graphene sheets from each other to prevent graphite formation during the process, but also determine the locally curved shape of graphene sheets. After removing Li2CO3, 3D graphene sheets with a honeycomb-like structure were obtained. This would be the first approach to synthesize 3D graphene sheets with a controllable shape. Furthermore, it has been demonstrated that the 3D Honeycomb-Structured Graphene (HSG) possesses excellent electrical conductivity and high catalytic activity. As a result, DSSCs with HSG counter electrodes exhibit energy conversion efficiency as high as 7.8%, which is comparable to that of an expensive noble Pt electrode.

Benzo1,2-b:4,5-b 'difuran-based sensitizers for dye-sensitized solar cells

Two BDF-based organic sensitizers, as first examples for their use in dye-sensitized solar cells, are prepared and characterized. They yield promising power conversion efficiencies of up to 5.5 and high open circuit voltages up to 0.82 V. This work demonstrates that the BDF chromophore acts as an effective donor in organic sensitizers.

A quinoxaline-fused tetrathiafulvalene-based sensitizer for efficient dye-sensitized solar cells

A new quinoxaline-fused tetrathiafulvalene-based sensitizer has been prepared and characterized. The resulting power conversion efficiency of 6.47% represents the best performance to date for tetrathiafulvalene-sensitized solar cells.

Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

Characterization of High-Performance Organic Dyes for Dye-Sensitized Solar Cell: A DFT/TDDFT Study

Dye-sensitized solar cell (DSSC) is currently a promising technology that makes solar energy efficient and cost-effective to harness. In DSSC, metal free dyes, such indoline-containing D149 and D205, are proved to be potential alternatives for traditional metal organic dyes. In this work, a DFT/TDDFT characterization for D149 and D205 were carried out using different functionals, including B3LYP, MPW1K, CAM-B3LYP and PBE0. Three different conformers for D149 and four different conformers for D205 were identified and calculated in vacuum. The performance of different functionals on calculating the maximum absorbance of the dyes in vacuum and five common solvents (acetonitrile, chloroform, ethanol, methanol, and THF) were examined and compared to determine the suitable computational setting for predicting properties of these two dyes. Furthermore, deprotonated D149 and D205 in solvents were also considered, and the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated, which elucidates the substitution effect on the rhodanine ring of D149 and D205 dyes on their efficiency. Finally, D149 and D205 molecules were confirmed to be firmly anchored on ZnO surface by periodic DFT calculations. These results would shed light on the design of new highly efficiency metal-free dyes.

Kinetics of electron recombination of dye-senitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO2 films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dye N719, C218 and D205 respectively have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τn, of the N719 based NR-DSSC is the lowest whereas the τn of the C218 based NR-DSSC is the highest among the three dyes. The higher Voc with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO2 film. In addition, in comparison to the DSSCs with conventional nanocrystalline particles based TiO2 films, the NR-DSSCs have shown over two orders of magnitude higher τn when employing N719 as the sensitizer. Nevertheless, the τn of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than the that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.

Heterogeneity in Dye-TiO2 Interactions Dictate Charge Transfer Efficiencies for Diketopyrrolopyrrole-Based Polymer Sensitized Solar Cells

Power conversion efficiency of a solar cell is a complex parameter which usually hides the molecular details of the charge generation process. For rationally tailoring the overall device efficiency of the dye-sensitized solar cell, detailed molecular understanding of photoinduced reactions at the dye-TiO2 interface has to be achieved. Recently, near-IR absorbing diketopyrrolopyrrole-based (DPP) low bandgap polymeric dyes with enhanced photostabilities have been used for TiO2 sensitization with moderate efficiencies. To improve the reported device performances, a critical analysis of the polymerTiO(2) interaction and electron transfer dynamics is imperative. Employing a combination of time-resolved optical measurements complemented by low temperature EPR and steady-state Raman spectroscopy on polymerTiO(2) conjugates, we provide direct evidence for photoinduced electron injection from the TDPP-BBT polymer singlet state into TiO2 through the C-O group of the DPP-core. A detailed excited state description of the electron transfer process in films reveals instrument response function (IRF) limited (<110 fs) charge injection from a minor polymer fraction followed by a picosecond recombination. The major fraction of photoexcited polymers, however, does not show injection indicating pronounced ground state heterogeneity induced due to nonspecific polymerTiO(2) interactions. Our work therefore underscores the importance of gathering molecular-level insight into the competitive pathways of ultrafast charge generation along with probing the chemical heterogeneity at the nanoscale within the polymerTiO2 films for optimizing photovoltaic device efficiencies.

Characteristics of Photo Electrodes Based on TiO2 Nanoparticles, Nanotubes and Microspheres for Dye Solar Cell

We have analyzed the characteristics of electrodes made of TiO2 nanotubes, microspheres and commercially available nanoparticles for dye sensitized solar cell. The morphology of the electrodes and the formation of aggregates have been analyzed by scanning electron microscopy and surface profiling technique. The concentration of Ti3+ type impurity state on the surface of these electrodes is quantified by X-ray photoelectron spectroscopy. Micro structural properties have been characterized by Brunauer, Emmett and Teller method The optical properties of the electrodes such as band gap energy, the type of band formation and the diffuse reflectance are evaluated by UV-Visible spectroscopy. The photovoltaic characteristics of dye solar cell made of these electrodes have been evaluated and it is found that the characteristics of the TiO2 film alone can alter the overall conversion efficiency to a great extent. Additional analysis using electrochemical impedance spectroscopy has been carried out to probe the electron transport properties and charge collection efficiency of these electrodes.

Synthesis and characterization of mesoporous TiO2 nanostructured films prepared by a modified sol-gel method for application in dye solar cells

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Fast hole surface conduction observed for indoline sensitizer dyes immobilized at fluorine-doped tin oxide - TiO2 surfaces

The indoline dyes D102, D131, D149, and D205 have been characterized when adsorved on fluorine-doped tin oxide (FTO) and TiO2 electrode surfaces. Adsorption from 50:50 acetonitrile - tert-butanol onto flourine-doped tin oxide (FTO) allows approximate Langmuirian binding constants of 6.5 x 10(4), 2.01 x 10(3), 2.0 x 10(4), and 1.5 x 10(4) mol-1 dm3, respectively, to be determined. Voltammetric data obtained in acetonitrile/0.1 M NBu4PF6 indicate reversible on-electron oxidation at Emid = 0.94, 0.91, 0.88, and 0.88 V vs Ag/AgCI(3 M KCI), respectively, with dye aggregation (at high coverage) causing additional peak features at more positive potentials. Slow chemical degradation processes and electron transfer catalysis for iodine oxidation were observed for all four oxidezed indolinium cations. When adsorbed onto TiO2 nanoparticle films (ca. 9nm particle diameter and ca.3/um thickness of FTO0, reversible voltammetric responses with Emid = 1.08, 1.156, 0.92 and 0.95 V vs Ag/AgCI(3 M KCI), respectively, suggest exceptionally fast hole hopping diffusion (with Dapp > 5 x 10(-9) m2 s-1) for adsorbed layers of four indoline dyes, presumably due to pie-pie stacking in surface aggregates. Slow dye degradation is shown to affect charge transport via electron hopping. Spectrelectrochemical data for the adsorbed indoline dyes on FTO-TiO2 revealed a red-shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near-IR region. The implications of the indoline dye reactivity and fast hole mobility for solar cell devices are discussed.

Dinuclear Ru-Cu complexes : electronic characterisation and application to dye-sensitised solar cells

Dye-sensitised solar cells have emerged as an important developing technology for low-cost solar energy conversion and a crucial element of these is the dye, responsible for light harvesting and control of interfacial electron-transfer processes.[1] A number of examples of dye exist in the literature which link a ruthenium polypyridyl complex to another platinum group metal complex such as Ru (II), Os (II), Re (I) or Rh (III) via a bridging ligand.[2-6] These systems are often referred to as heterosupramolecular triads when adsorbed on the surface of TiO2 as the semiconductor becomes an active component in the system. A number of problems can arise with these types of sensitisers, for example if a flexible linker, e.g. bis-pyridylethane, is used to couple the two complexes it can be hard to control the orientation of the whole dye. This may lead to the resultant dye cation hole being closer to the surface than desired, and hence the long-lived charge-separated state is not achieved. In addition the size of these dyes may be much larger than that of a mononuclear complex and can lead to poor pore filling on the TiO2 and lower dye coverage, leading to a lower efficiency cell.[7] Despite these issues, efficient charge-separation has been achieved with polynuclear complexes and a long-lived state on the millisecond timescale has been observed for a trinuclear ruthenium complex.[8]

An ultraviolet selective photodetector based on a nanocrystalline TiO2 photoelectrochemical cell

Solar ultraviolet (UV) radiation causes a range of skin disorders as well as affecting vision and the immune system. It also inhibits development of plants and animals. UV radiation monitoring is used routinely in some locations in order to alert the population to harmful solar radiation levels. There is ongoing research to develop UV-selective-sensors [1–3]. A personal, inexpensive and simple UV-selective-sensor would be desirable to measure UV intensity exposure. A prototype of such a detector has been developed and evaluated in our laboratory. It comprises a sealed two-electrode photoelectrochemical cell (PEC) based on nanocrystalline TiO2. This abundant semiconducting oxide, which is innocuous and very sta-ble, is the subject of intense study at present due to its application in dye sensitized solar cells (DSSC) [4]. Since TiO2 has a wide band gap (EG = 3.0 eV for rutile and EG = 3.2 eV for anatase), it is inher-ently UV-selective, so that UV filters are not required. This further reduces the cost of the proposed photodetector in comparison with conventional silicon detectors. The PEC is a semiconductor–electrolyte device that generates a photovoltage when it is illuminated and a corresponding photocur-rent if the external circuit is closed. The device does not require external bias, and the short circuit current is generally a linear function of illumination intensity. This greatly simplifies the elec-trical circuit needed when using the PEC as a photodetector. DSSC technology, which is based on a PEC containing nanocrystalline TiO2 sensitized with a ruthenium dye, holds out the promise of solar cells that are significantly cheaper than traditional silicon solar cells. The UV-sensor proposed in this paper relies on the cre-ation of electron–hole pairs in the TiO2 by UV radiation, so that it would be even cheaper than a DSSC since no sensitizer dye is needed. Although TiO2 has been reported as a suitable material for UV sensing [3], to the best of our knowledge, the PEC configuration described in the present paper is a new approach. In the present study, a novel double-layer TiO2 structure has been investigated. Fabrication is based on a simple and inexpensive technique for nanostructured TiO2 deposition using microwave-activated chemical bath deposition (MW-CBD) that has been reported recently [5]. The highly transparent TiO2 (anatase) films obtained are densely packed, and they adhere very well to the transparent oxide (TCO) substrate [6]. These compact layers have been studied as contacting layers in double-layer TiO2 structures for DSSC since improvement of electron extraction at the TiO2–TCO interface is expected [7]. Here we compare devices incorporating a single mesoporous nanocrystalline TiO2 structure with devices based on a double structure in which a MW-CBD film is situated between the TCO and the mesoporous nanocrystalline TiO2 layer. Besides improving electron extraction, this film could also help to block recombination of electrons transferred to the TCO with oxidized species in the electrolyte, as has been reported in the case of DSSC for compact TiO2 films obtained by other deposition tech-niques [8,9]. The two types of UV-selective sensors were characterized in detail. The current voltage characteristics, spectral response, inten-sity dependence of short circuit current and response times were measured and analyzed in order to evaluate the potential of sealed mesoporous TiO2-based photoelectrochemical cells (PEC) as low cost personal UV-photodetectors.