Linear and Time-Resolved THz Spectroscopy of Photonic and Charge Transporting Systems

Photo-induced charge separation and charge transport are fundamental processes in many energy conversion techniques, where light is converted into chemical energy (PEC), into electrical energy (solar cells) or in the opposite sense if electrical energy is converted into light (LEDs). In all cited examples, charge carriers have either to be transported towards an interface where they can undergo radiative recombination, trigger a chemical reaction, or they have to be evacuated from the interface as free charge carriers to be able to perform work in an external electrical circuit. In this work the charge generation dynamics and transport is studied using THz time domain spectroscopy and complimentary techniques on systems finding application in dye sensitized solar cells and PEC cells for water splitting. The functioning of a dye sensitized solar cell is based on the kinetic competition between several reactions, i.e. electron injection, dye-regeneration, electron back- reaction and charge extraction. Accordingly the rates of all of these reactions have to be optimized in order to optimize the cell performance. This requires a good understanding of the underlying mechanism of these processes. In photochemical cells, the encountered processes are in a way similar. After initial excitation, the generated charges have to be separated and have to reach either the interface to the electrolyte or the external circuit before being annihilated by recombining. Knowing the diffusion length and carrier lifetime in a specific material might therefore be helpful to optimize the film morphology, i. e. the aspect ratio. Chapter 1 gives an overview over the functioning of DSCs and PEC cells and summarizes some theoretical aspects of the processes encountered in these devices. Chapter 2 is devoted to the description of the experimental tools used and built in this work. In chapter 3, charge transport in a liquid molecular hole conductor, 10- methylphenoxazine, is investigated. The transport is rationalized using a model taking into account ionic diffusion and intermolecular hole transfer, i. e. hopping. It is found that the conduction occurs principally by hopping, as the HTM cation seems to be mainly present in an ion-paired form with the anion from the doping agent. Hopping of charge requires molecular vibration to bring acceptor and donor molecule in electronic resonance. Two vibrational modes of the HTM cation and neutral molecules that might be coupled to charge transport are observed. In chapter 4, electron injection from a dye into the conduction band of TiO2 films is investigated by monitoring the appearance of the free electron. This signal is compared to the signal arising from direct UV excitation of the TiO2. In addition to previous studies done in the group, the effect of dye aggregation leading to decelerated electron injection is investigated. Comparing the THz signal amplitude to the injected charge carrier concentration, the THz mobility in TiO2 films was found to be 0.1-0.15 cm2V-1s-1 and constant over the investigated charge carrier concentrations. Furthermore the influence of sintering temperature of the TiO2 film has been addressed in a preliminary study. In chapter 5, the influence of liquid electrolytes, of a solid state hole conducting material and of the commonly used additives Li+ and tBP on the charge generation dynamics have been investigated. While in this work the presence of an electrolyte/HTM has not shown any influence on the electron injection dynamics, the generation of the free electron seems to be strongly dependent on the molecular surrounding. This discrepancy is discussed in terms of a coulombic bound electron- hole pair as an intermediate state in the electron injection dynamics. Chapter 6 contains a study on the charge carrier dynamics in cuprous oxide, being used as material for photoelectrochemical water splitting. The wavelength and fluence dependence on the charge carrier lifetime, mobility and diffusion length was studied. The strong dependence of the charge carrier lifetime is discussed in terms of trapping mediated recombination.

Solar Energy Stored as Hydrogen

Jérémie Minh-Châu Brillet

The tandem photoelectochemical (PEC) cell based on oxide semiconductors for water splitting offers a potentially inexpensive route for solar hydrogen generation. At the heart of the device, a nanostructured photoanode for water oxidation is connected in series with one or two dye-sensitized solar cells (DSCs) that provide an extra bias to photogenerated electrons in order to perform water reduction at the platinum cathode. In Part A of this thesis, after reviewing the different technologies available for solar hydrogen production, I focus on different possible architectures for photoanode / DSC tandem cells enabled by the most recent advances in the field. First, the development of all organic squaraine dyes having a narrow absorption bandwidth extending into the near infrared region and a broad transparent window in the visible region of the spectrum have allowed the design of a new photoanode / DSC / DSC tandem architecture. The "Back DSC" tandem cell, where two DSCs placed side-byside exploit the photons transmitted by a single photoanode is the conventional architecture. In this thesis, I demonstrate the inverted "Front DSC" architecture, which allows the use of non-transparent lower cost metallic substrate for the photoanode, as well as the "tri-level" tandem cell where a panchromatic "black" dyebased DSC exploits the energy transmitted by the photoanode and the squaraine dyebased DSC. Opto-electronic studies on each of these three architecture are performed and the respective solar-to-hydrogen conversion (STH) efficiencies of 1.16 %STH, 0.76 %STH and 1.36 %STH are assessed. Finally, I leverage recent findings in the field of high voltage DSCs to demonstrate for the first time a tandem cell using only one photovoltaic cell to perform complete water splitting at efficiencies as high as 3.10 % STH. Such a result represents a ten-fold improvement over previous demonstrations with this class of device. This work describes a breakthrough in the inexpensive solar-to-chemical conversion using improved photon management in a dual-absorber tandem cell and undoubtedly constitutes a benchmark for solar fuel production by solution processable oxide-based devices. In Part B, I focus on the photoanode for the oxygen evolution reaction. Hematite (α-Fe2O3) is a great candidate material for this application due to its availability, low cost, non-toxicity and appropriate band gap allowing extensive absorption in the visible part of the spectrum. However, it suffers severe drawbacks, among which are poor majority carrier conductivity and a short diffusion length of minority charge carrier with regard to photon penetration depth. This circumstance causes most photogenerated charges to have a low probability of reaching the semiconductor / liquid junction and thus to participate in the water oxidation reaction. This feature implies the use of hematite morphologies having feature size in the range of 10-20 nm. A solution-based colloidal approach offers a simple and easily scalable method to obtain nanostructured hematite. However, this type of nanostructure needs to be exposed to an annealing step at 800 °C to become photoactive. This has been attributed to the diffusion of dopants from the substrate. In addition, this annealing step sinters the 10 nm particles colloid into a feature size approaching 100 nm. Here, I first show the effect of intentionally doping this material on the sintering and photoactivity. I then demonstrate a method that allows for the first time to apply high temperature annealing steps while controlling the feature size of the nanoparticles. Such an approach can be applied to any kind of nanostructure. This latter strategy coupled to further passivation of surface states allowed an improvement of the net photoactivity of this type of photoanode by a factor of two. A reproducible net photocurrent exceeding 4 mA.cm-2 was obtained. This result represents the highest performance reported for hematite under one sun illumination. In Part C of this thesis, I present several synthesis methods for titania nanostructures acting as photoanodes in the DSC. In this photovoltaic cell, the electronic loss that is typically discussed is the slow transport induced recombination. Charges recombining before reaching the electrode have a detrimental influence on the photocurrent and photovoltage. Several approaches have been proposed in order to reduce interfacial recombination and improve charge collection in liquid electrolyte and solid state-DSCs (ss-DSCs) including the use of radial collection nanostructures, one-dimensional ZnO and TiO2 nanorods, and nanowires as photoanodes. Even though these approaches show great promise, they have yet to achieve power conversion efficiencies above 5% in liquid electrolyte DSCs and 1.7% in ss-DSCs. In this part of my thesis, I expose results on the strategies I have pursued during the course of my PhD to improve the dynamics in the liquid and ss-DSC. From one dimensional titania nanotube arrays, I have moved to tri-dimensional fibrous network of crystalline TiO2 and more complex host-passivation-guest photoelectrodes.

EPFL2012

Electronic and structural modification of titanium dioxide/zinc oxide photoanode for dye-sensitized solar cells

Aravind Kumar Chandiran

Dye-sensitized solar cells (DSC) are a new class of molecular photovoltaics that mimics the natural photosynthesis, for the direct conversion of sunlight into electricity. A typical DSC is a sandwich of a dye sensitized nanoparticle TiO2 film and a catalyst coated counter electrode, with a redox electrolyte filling the space in between. The high internal surface area of the mesoporous TiO2 film ensures higher dye uptake for an efficient light harvesting. Following the light illumination, an electron from the highest occupied molecular orbitals (HOMO) of the dye is excited to its lowest unoccupied molecular orbitals (LUMO). Due to an effective electronic orbital coupling between dye and TiO2, the excited electrons are injected into TiO2. The oxidized dye is regenerated by the electron donor present in the electrolyte. The circuit is completed by the transfer of photogenerated electrons in TiO2 via an external load, to counter electrode regenerating the oxidized electrolyte species. In a conventional DSC, the transport rate of the photogenerated electrons in TiO2 competes with the parasitic electron recombination, as these two processes occur at a similar ms time domain. This thesis work is aimed at the fundamental understanding of these electron transfer processes at sensitized photoanodes that were subject to different bulk and surface electronic structural modifications. The implications were shown to be of profound interest for the fabrication of high efficiency and low cost dye-sensitized solar cells. In the first part of the thesis, the bulk electronic structure of the anatase TiO2 nanoparticles is modified by the incorporation of different concentrations of aliovalent cations (Nb5+, Ga3+, Y3+) in the crystal lattice. The cationic doping/substitution in the nanoparticles is achieved by hydrothermal process. The modified nanoparticles retained the parent anatase crystal structure of TiO2. The transparent dye-sensitized solar cells made with these modified films, using our standard heteroleptic metal complex sensitizers and iodide/triiodide redox electrolyte, displayed enhanced photovoltaic performances, at certain added concentrations. Charge extraction measurements in DSC, reveals a formation of deeper trap states below the conduction band of titanium dioxide when Nb ion is incorporated into the TiO2 lattice. On the other hand, Ga3+ and Y3+ did not significantly affect the trap states distribution compared to the reference device. The modification in the trap states and the oxygen stoichiometry due to these cation inclusions significantly influenced the electron recombination and transport rates. These properties are investigated in detail using transient decay techniques. Following the study on the electronic structure of the bulk TiO2, the influence of the surface modification of the TiO2 nanoparticles on the electron transfer dynamics is investigated. The kinetics of electron recombination from TiO2 to the single electron redox shuttles is fast, leading to a significant loss in the open-circuit potential (VOC) of devices. The emergence of cobalt complexes as a potential electrolyte motivated us to investigate the role of surface passivation of the titanium dioxide nanoparticles. Insulating sub-nanometer oxide tunneling layers deposited by atomic layer deposition (ALD) are known to block the electron recombination, thereby, leading to an increase in the VOC and the collection efficiency of the solar cell. A general perception in the DSC community is that any insulating oxide layer can block the recombination. However, in this work, it is unraveled that, just the insulating property of oxides is not sufficient. In addition, the properties such as the conduction band position and the oxidation state of the insulating oxide, the electronic structural modification induced to the underlying TiO2 mesoporous film, modification of surface charges (isoelectric point) and charge of the electrolyte species have to be considered. A complete photovoltaic study has been done by depositing different cycles (by ALD) of four insulating oxides (Ga2O3, ZrO2, Nb2O5 and Ta2O5) and their recombination characteristics, surface electronic properties, transport rate and injection dynamics are investigated with a standard organic dye and Co2+/Co3+ redox mediator. A comparison is made with the conventional iodide/triiodide electrolyte. The second part of the thesis is focused at the development of new type of photoanodes for effective electron transport to increase the charge collection efficiency. We present a way of utilizing thin and conformal overlayer of titanium dioxide or zinc oxide on an insulating mesoporous template as a photoanode for dye-sensitized solar cells. Different thicknesses of TiO2 ranging from 1 to 15 nm are deposited on the surface of the template by ALD. This systematic study helps unraveling the minimum critical thickness of the TiO2 overlayer required to transport the photogenerated electrons efficiently. A merely 6 nm thick TiO2 film on a 3 μm mesoporous insulating substrate is shown to transport 8 mA/cm2 of photocurrent density along with ≈900 mV of open-circuit potential, when using our standard donor-π-acceptor sensitizer and Co(bipyridine)3 redox mediator. The three dimensional conformal shell on the insulating core also exhibits one order of magnitude higher transport rate compared to the conventional TiO2 nanoparticles. Similar nanostructures were made by depositing ZnO on an insulating template and the electron transfer properties are compared with titania. We also developed ALD recipe for the deposition of crystalline TiO2 or ZnO at low temperatures (< 200 °C) on arbitrary mesoporous insulating templates, considering their prospects of making photoanodes on flexible plastic substrates. The experience gained about the deposition of conformal and pin-hole free TiO2 layer in the previous section is extended for the high efficiency solid-state mesoscopic solar cells based on CH3NH3PbI3 perovskite absorbers. We show that a 2 nm as-deposited ALD overlayer on a mesoporous TiO2 film, printed on a bare conducting glass, is sufficient to arrest the recombination process that lead to a power conversion efficiency of 11.5 %. A detailed investigation on the electron back reaction is presented using electrochemical impedance spectroscopy.

EPFL2013

Strategies to Optimizing Dye-Sensitized Solar Cells

Sophie Wenger

Dye-sensitized solar cells (DSCs) constitute a novel class of hybrid organic-inorganic solar cells. At the heart of the device is a mesoporous film of titanium dioxide (TiO2) nanoparticles, which are coated with a monolayer of dye sensitive to the visible region of the solar spectrum. The role of the dye is similar to the role of chlorophyll in plants; it harvests solar light and transfers the energy via electron transfer to a suitable material (here TiO2) to produce electricity — as opposed to chemical energy in plants. DSCs are fabricated of abundant and cheap materials using inexpensive processes (e.g. screen-printing) and are likely to be a significant contributor to the future commercial photovoltaic technology portfolio. The work conducted during this thesis aimed at optimizing the DSC using three different strategies: The use of versatile organic sensitizers for stable and efficient DSCs, the study of tandem device architectures in combination with other solar cells to harvest a larger fraction of the solar spectrum, and the development of a validated optoelectric model of the DSC. Organic donor-π-acceptor dyes are an interesting alternative to the standard metal-organic complexes used in DSCs. Efficient photovoltaic conversion and stable performance could be demonstrated with three classes of donor systems, namely diphenylamine, difluorenylaminophenyl, and π-extended tetrathiafulvalene. The highest conversion efficiencies were obtained with a difluorenylaminophenyl donor system (η = 8.3 % with a volatile electrolyte and η = 7.6 % with a solvent-free ionic liquid, which was a new record for organic dyes at the time of publication). Surprisingly, efficient regeneration of the oxidized dye by the I-/I3- redox mediator was found with the π-extended tetrathiafulvalene system, even though the thermodynamic driving force was as low as 150 mV. So far driving forces of 300-500 mV had been regarded as necessary for efficient regeneration of the dye cation. Also, important structure-property relationships pertaining to the recombination of electrons with the electrolyte and to the stability of the device could be identified (i.e. effect of linear vs. branched structure, linker length, and moieties used). The power conversion efficiency of solar cells can be extended beyond the limit for a single cell (∼ 30 %) by using multiple cells with different optical gaps in a tandem device. DSCs and chalcopyrite Cu(In,Ga)Se2 (CIGS) solar cells have complementary optical gaps and are thus suitable systems for integration in a tandem device. It was shown that a monolithic DSC/CIGS tandem device has the potential for increased efficiency over a mechanically stacked device due to increased light transmission to the bottom cell, and a monolithic DSC/CIGS device with an initial efficiency of η = 12.2 % was demonstrated. The degradation of the devices — induced by the corrosion of the CIGS cell in contact with the I-/I3- redox mediator — could be retarded with a protective thin conformal ZnO/TiO2 oxide layer coated on the CIGS cell by atomic layer deposition. Finally, an experimentally validated optical and electrical model of the DSC has been developed to assist the optimization process, which is predominantly conducted by empirical means in the DSC research community. The optical model allows to accurately calculate the internal quantum efficiency of devices, i.e. the ratio of extracted electrons to absorbed photons by the dye, a crucial and so far difficult to determine characteristic. Intrinsic parameters — like injection efficiency, electron diffusion length, or distribution of trap states in the TiO2 — can be extracted from experimental steady-state and time-dependent data with the electric model. The model allows to make a comprehensive and quantitative loss analysis of the different optical and electric loss channels in the DSC. The model has been implemented with a graphical user interface for straightforward usage. All three optimization strategies — organic dyes, tandem architecture, and device modeling — developed during this thesis make a valuable contribution to the development and commercialization of inexpensive and high efficiency DSCs. They enable a comprehensive view of the system and pave the way for a systematic analysis and reduction of losses, which has been the ultimate route to success for several established photovoltaic technologies.

EPFL2010