Exciton Dynamics in 2D Organic Assemblies for Realization of Next-generation Optoelectronic Devices

Supramolecular assemblies of cyanine dye molecules formed by weak van der Waals forces have gained immense attention for their distinct optical properties (high extinction coefficient, narrow absorption and photoluminescence line-width and small Stokes shift) compared to their monomer counterparts. Strong light-matter interaction in the J-aggregates causes coherent exciton migration and high color purity emission. This motivates to fabricate J-aggregate thin films for different opto-electronic devices such as solar cells, where J-aggregates serve as exciton transport channels, organic light emitting diodes (OLEDs) and polariton lasers. Exciton migration and photoluminescence quantum yield (PLQY) of the J-aggregates in thin films dictate the efficiency of energy harvesting and light emitting devices, respectively. The main focus of this thesis is the development of a new J-aggregate growth route which favors the formation of large, coherent domains of 2D J-aggregate thin films and to investigate the exciton dynamics. Furthermore, non-radiative decay channels suppressing the PLQY of J-aggregates in thin film and in solution were identified. The coherent crystalline domain size in thin films is typically limited to nanoscale length because dye molecules spontaneously self-assemble already in solution. This can be overcome by maintaining equilibrium between monomers and the critical nucleus of a J-aggregate in solution. This approach is shown here as a successful route to achieve large coherent domains on a functionalized substrate. The growth model was further confirmed with small-angle x-ray scattering (SAXS) studies. Using time-resolved photoluminescence (TRPL) spectroscopy, non-radiative decay channels limiting the exciton migration were identified. The results suggest that the increase in domain size and order is directly proportional to the increased radiative decay of the excitons. Furthermore, the PLQY of J-aggregates in water at room temperature is typically ~5%. Upon addition of alkylamine, the quantum yield was drastically improved while maintaining line-width and peak position. Using small-angle neutron scattering (SANS), a two-phase region was identified in the water-dye-alkylamine ternary phase diagram in which high PLQY J-aggregates form. From TRPL studies, an increase in radiative lifetime is in agreement with the increase in PLQY. As an application, ultra-narrowband photodetectors were explored owing to the narrow line-width of J-aggregate absorption. The concept proved advantageous over other strategies for narrowing the response width, with competing figure of merits. Realization of an inkjet printed prototype with higher frequency response compared to spin-coated devices highlights their potential for industrial applications. Excitonic channels using J-aggregate nanowires were formed by complexing J-aggregates with dendronized polymers. SAXS studies revealed a core-shell configuration of the DP-J-aggregate hybrid structure. A correlation between polymer conformation and J-aggregates allowed to assemble J-aggregate nanowires as thin films. Centrosymmetric cyanine dimers are known for their non-luminescent nature. Twisted dimer packing of dye molecules in a polymer matrix are confirmed from circular dichroism spectroscopy studies. This explains a strongly red-shifted photoluminescence with high quantum yield in the thin film.

Dynamics of Electronic and Ionic Charges in Cyanine Organic Semiconductor Devices

Sandra Christina Jenatsch

Organic semiconductor materials have been widely applied in optoelectronic devices to replace their inorganic counterparts and explore new fields of applications. Due to their high extinction coefficients, chemical tunability and solubility, cyanine dyes are an interesting class of molecules to be employed in organic semiconductor devices. Their beneficial properties have been demonstrated in organic solar cells (OSC), photodetectors and recently in organic light-emitting electrochemical cells (OLEC). The focus of this thesis is to analyse different aspects regarding the dynamics of electronic and ionic charges in cyanine based devices. Models and conclusions are not restricted to cyanine based devices but can potentially be applied in various systems where combined ionic and electronic charges are present. In order to focus on electronic processes in OSCs, a combination of steady-state, transient and impedance analysis is used. It is resolved that trapped charges can be introduced at the dye/hole extracting layer interface by using specific solvents for the cyanine layer fabrication. These measurements also reveal the low hole mobility of cyanine films which in turn limits the possible upper layer thickness in OSCs. A frequently used way to enhance the conductivity of organic semiconductors is the addition of extra charges by chemical doping. This concept is employed for a near-infrared absorbing dye which is used as donor in a bilayer solar cell. The dependence of all figures of merit versus doping concentration and layer thickness is studied in detail. It is found that the performance of the optimised cell is not further improved by doping, but that it presents a good option if thicker layers are required, e.g. on rough substrates. Furthermore, the stability and degradation pathway of the p-doped species is analysed. This information is of general relevance as they also occur after charge transfer at the heterojunction interface of an OSC and during operation of OLECs. The dynamics of ionic charge carriers is separated into two contributions. In a first step, the steady-state diffusion profile of the counter ion within a cyanine/fullerene bilayer structure is scrutinised using different profiling techniques. An unexpected constant ion profile is found throughout the C60 layer. Simultaneously, the potential within the acceptor is measured by the Kelvin probe technique. A mechanism of combined electron and ion transfer from the C60 to the dye and vice versa is proposed which is in agreement with the experimental results. A prerequisite for OLEC operation is the mobility of ionic charge carriers. Their dynamics in cyanine salts under the effect of an external field is therefore studied in such devices. Several methods are developed and applied to characterise the dynamic p-i-n structure in detail, i.e. the position and width of the intrinsic region as well as the doping concentrations in p- and n-doped regions. The combination of all these methods helps to understand the transient behaviour of these cyanine devices but can also be adapted to other OLEC systems. A major drawback of cyanine dyes as emissive material is their low fluorescence quantum yield in solid films. To overcome this restriction and improve the OLEC efficiency, host-guest systems with various visibly emitting dyes are studied. The gain in fluorescence quantum yield in the film can directly be transferred to an increase in external quantum efficiency of the device.

EPFL2017

Terahertz Time-Domain Spectroscopy Study of the Conductivity of Hole-Transporting Materials

Jan Cornelius Brauer, Jacques-Edouard Moser, Verner Thorsmolle

Some redox-active ionic liquids, organic amorphous solids containing electron-donating moieties, and conductive polymers can efficiently transport positive electrical charges. These hole-conducting media find increasing applications in unconventional solar cells and organic light-emitting diodes. Appropriate methods are required to unravel the detailed conduction and trapping mechanisms in these materials as well as to fully understand the interplay of molecular vibrations and charge transport processes. Here we present terahertz time-domain spectroscopy (THz-TDS) as a powerful technique, that allows the direct determination of the complex conductivity of hole transporting materials in a contactless, purely optical manner. Beyond the measurement of the conductivity of solid and liquid materials, THz (far infrared) spectroscopy also provides direct information of the librational and vibrational modes coupled to charge transport processes and therefore is invaluable in the study of the mechanism of polaronic transport in matter. Application of this technique is illustrated by examples provided by the study of the ionic liquid 3-methyl-1-propylimidazolium bis(trifluoromethane) sulfonimide (PMIT FSI) and that of the molecular liquid hole conductor 10-methylphenoxazine. Both systems are of particular interest, as both types of holetransporting media are successfully used as alternatives to solvent-based electrolytes in dye sensitized solar cells

Schweizerische Chemische Gesellschaft2009

Nanoparticle sensitisation of solid-state nanocrystalline solar cell

Robert Plass

Over the past fifteen years dye-sensitised nanocrystalline solar cells have been the subject of intense research and development efforts. These systems provide a technically and economically credible alternative to classical p-n junction solar cells, reaching over 10 % certified efficiency under standard solar illumination conditions (AM 1.5, 1000 W/m2). Recently, the liquid electrolyte, commonly used in these dye-sensitised solar cells, could successfully be replaced by a novel solid hole-conducting material (spiro-OMeTAD). The absence of volatile solvents and corrosive components like iodine presents a clear advantage of these solid-state devices over their photoelectrochemical counterparts. Yet, their maximum overall efficiency of about 3 % clearly lacks behind the performance features of classical dye-sensitized solar cells. The objective of this work is the replacement of the usually used sensitiser (transition metal complexes and organic dyes) by quantum-dots. It was motivated by the possibility to achieve panchromatic light absorption due to the size-dependent properties of the quantum-dots. Some studies have been published using quantum-dots of inorganic low-bandgap semiconductors as sensitisers for mesoporous wide bandgap semiconductor electrodes in conjunction with liquid electrolytes. These systems often suffer from corrosion and photo-corrosion mainly due to the aggressive nature of the electrolyte employed. Solid-state organic-inorganic heterojunctions might provide the desired environment for quantum-dot sensitisation, as the environment is much less aggressive. A large variety of inorganic quantum-dot materials like PbS, CdS, PbSe and CdSe were scrutinized for their use as sensitisers. All particles were synthesised in situ on the TiO2 surface using two different techniques: dip-coating and chemical bath deposition. Lead sulphide was the most investigated due to its superior photovoltaic characteristics. High Resolution Transmission Electron Microscopy (HRTEM) of PbS sensitised TiO2 electrodes fabricated via dip-coating clearly showed the distinct particles on the surface of the semiconductor. The electron transfer dynamics following optical excitation of quantum-dot sensitized TiO2/spiro-OMeTAD heterojunctions were thoroughly studied. Fluorescence spectroscopy was used to prove the possible electron injection from the PbS into the TiO2. Nanosecond laser spectroscopy was applied to monitor the interfacial recombination of the injected electron and the oxidised hole-conductor. Femtosecond laser spectroscopy allowed measuring the ultra-fast kinetics in the system, including electron trapping, exciton recombination and PbS regeneration. An overall efficiency of 0.5 % at 0.1 sun (AM 1.5) has been reached with such systems. Chemical bath deposition (CBD) of PbS leads to the formation of a layer rather than distinct particles on the TiO2. Solar cells fabricated via CBD exhibited open-circuit voltages which were generally 100 mV higher then those of comparable devices made via dip-coating. The PbS layer acts as blocking layer, hindering the contact between TiO2 and the hole-conductor. This technique allowed achieving devices highly linear with respect to the illumination power. Different strategies were pursued to impede interfacial recombination, among which the introduction of self-assembled monolayers at the interface between the organic and inorganic phases was proven to be the most efficient. Nanosecond laser spectroscopy showed a strong decrease of the interfacial recombination kinetic rates in the presence of hexadecylmalonic acid or decylphosphonic acid monolayers. Short-circuit currents could be raised by a factor two to four using such type of molecules. The overall efficiency of the device could be strongly increased, reaching 1 % at 0.1 Sun (AM 1.5). CBD was also used to deposit PbSe and CdSe layers at the surface of TiO2. Fluorescence spectroscopy was used to probe electron injection from CdSe quantum dots to TiO2. Generally it was observed that metal sulfides were more efficient in sensitizing TiO2/OMeTAD heterojunctions then the respective selenides.