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Singlet fission and triplet–triplet annihilation represent two highly promising ways of increasing the efficiency of photovoltaic devices. Both processes are believed to be mediated by a biexcitonic triplet-pair state, 1(TT). Recently however, there has been debate over the role of 1(TT) in triplet–triplet annihilation. Here we use intensity-dependent, low-temperature photoluminescence measurements, combined with kinetic modelling, to show that distinct 1(TT) emission arises directly from triplet–triplet annihilation in high-quality pentacene single crystals and anthradithiophene (diF-TES-ADT) thin films. This work demonstrates that a real, emissive triplet-pair state acts as an intermediate in both singlet fission and triplet–triplet annihilation and that this is true for both endo- and exothermic singlet fission materials.The role of the biexcitonic triplet-pair state 1(TT) during triplet–triplet annihilation events in singlet-fission materials has been the subject of recent debate. Now, emissive 1(TT) states have been shown to be direct products of triplet–triplet annihilation in both endothermic and exothermic singlet-fission materials.

We investigated and optimised the performance of the all-optical reflective modulation of the Mid-Wave Infrared (MWIR) signal by means of the optically-pumped sub-wavelength-structured optical membranes made of silicon. The membranes were optically pumped by a 60-femtosecond, 800-nm laser, while another laser operating in the MWIR ranging between 4 and 6 μ m was used to probe the optical response and modulation. We were able to achieve the conditions providing the modulation depth of 80% using the pump fluence of 3.8 mJ/cm 2 . To get a better insight into the performance and the modulation mechanism, we developed an optical model based on a combination of the Wentzel–Kramers–Brillouin approximation, Drude and Maxwell–Garnett theories. The model allowed us to estimate the values of the dielectric function, carrier concentration and scattering rate of the optically-excited membrane in the MWIR range. Using the model, we optimised the performance and found the conditions at which the reflective modulation can be operated with the ultrafast response of 0.55 ps and modulation contrast of 30%.

We demonstrate for the first time the possibility of all-optical modulation of self-standing porous Silicon (pSi) membrane in the Mid-Wavelength Infrared (MWIR) range using femtosecond pump-probe techniques. To study optical modulation, we used pulses of an 800 nm, 60 femtosecond for pump and a MWIR tunable probe in the spectral range between 3.5 and 4.4 μm. We show that pSi possesses a natural transparency window centred around 4 μm. Yet, about 55% of modulation contrast can be achieved by means of optical excitation at the pump power of 60 mW (4.8 mJ/cm 2 ). Our analysis shows that the main mechanism of the modulation is interaction of the MWIR signal with the free charge carrier excited by the pump. The time-resolved measurements showed a sub-picosecond rise time and a recovery time of about 66 ps, which suggests a modulation speed performance of ~15 GHz. This optical modulation of pSi membrane in MWIR can be applied to a variety of applications such as thermal imaging and free space communications.

Two novel cyclometallated iridium(III) complexes have been prepared with one bidentate or two monodentate imidazole-based ligands, 1 and 2, respectively. The complexes showed intense emission with long lifetimes of the excited state. Femtosecond transient absorption experiments established the nature of the lowest excited state as 3IL state. Singlet oxygen generation with good yields (40% for 1 and 82% for 2) was established by detecting 1O2 directly, through its emission at 1270 nm. Photostability studies were also performed to assess the viability of the complexes as photosensitizers (PS) for photodynamic therapy (PDT). Complex 1 was selected as a good candidate to investigate light-activated killing of cells, whilst complex 2 was found to be toxic in the dark and unstable under light. Complex 1 demonstrated high phototoxicity indexes (PI) in the visible region, PI > 250 after irradiation at 405 nm and PI > 150 at 455 nm, in EJ bladder cancer cells.

A Correction to this paper has been published: https://doi.org/10.1038/s41557-020-00622-w

This thesis is devoted to the experimental investigation of ultrafast dynamics in silicon nanostructures and surface plasmonics by means of femtosecond lasers. First part of the research, ultrafast carriers dynamics in silicon nano-structures, is based on the time-resolved pump-probe reectivity method. A change in the density of excited carriers, as a response to the change of the excitation intensity, was extracted from the time-resolved re ectivity of crystalline nanopillars and nano-inclusions. The measurements were performed mainly in the sub-melting uence regime, at nearly normal incidence to the sample surface plane of the pump and probe beams. Both types of nano-structures have shown strong intensity dependent response comparing to bulk crystalline silicon. This enhanced response is attributed to a suppression of the diffusion processes in nanopillars and nonlinear response due to a constructive multilayer interference between the host matrix material, where silicon inclusions have been embedded, and the sublayers. Electron-phonon and recombination characteristic decay-times are extracted. The second part is devoted to sub-nanosecond decay of photoluminescence from siliconnitride amorphous structures. Particular structures have shown two radiative decay peaks. The second radiative peak is addressed to deep subband tail states, originated by the open bonds of the amorphous structure leading to the long radiative transition. The last part describes femtosecond-resolved plasmon-assisted dissociation of diatomic oxygen molecules in ultrahigh vacuum conditions. Asymmetric gold gratings have been utilised to create enhanced local electric elds originated from the optically excited surface plasmon resonances. Charged products of the dissociation process have been analysed by time-of-light linear drift mass spectrograph, while two-dimensional distribution has been achieved deploying Velocity Map Imaging technique. The dissociation process is found intensity dependent with strong non-linear prole. No correlation has been observed with background plasmon-enhanced electron emission.

Singlet exciton fission is the spin-allowed generation of two triplet electronic excited states from a singlet state. Intramolecular singlet fission has been suggested to occur on individual carotenoid molecules within protein complexes, provided the conjugated backbone is twisted out-of-plane. However, this hypothesis has only been forwarded in protein complexes containing multiple carotenoids and bacteriochlorophylls in close contact. To test the hypothesis on twisted carotenoids in a 'minimal' one-carotenoid system, we study the orange carotenoid protein (OCP). OCP exists in two forms: in its orange form (OCPo), the single bound carotenoid is twisted, whereas in its red form (OCPr), the carotenoid is planar. To enable room-temperature spectroscopy on canthaxanthin-binding OCPo and OCPr without laser-induced photoconversion, we trap them in trehalose glass. Using transient absorption spectroscopy, we show that there is no evidence of long-lived triplet generation through intramolecular singlet fission, despite the canthaxanthin twist in OCPo.

The orange carotenoid protein (OCP) is the water-soluble mediator of non-photochemical quenching in cyanobacteria, a crucial photoprotective mechanism in response to excess illumination. OCP converts from a dark-adapted inactive state (OCPo) to an active quenching conformation (OCPr) under high-light conditions, resulting in a concomitant redshift in the absorption of the bound carotenoid. Here, we test whether a long-lived carotenoid singlet excited state (S*) is required for this photoconversion. We measured pump wavelength-dependent transient absorption of OCPo trapped in trehalose-sucrose glass films. We found that initial OCP photoproducts are still formed despite the glass preventing completion to OCPr, and that S* is only apparent for <495 nm pumps. By comparison to the pump wavelength-dependence of the OCPo to OCPr conversion in buffer, we show that S* is not required for photoconversion, and that S* likely arises from ground-state heterogeneity within OCPo.

Singlet fission (SF), the spin-allowed conversion of one singlet exciton into two triplet excitons, offers a promising strategy for enhancing the efficiency of photovoltaic devices. However, realising this potential necessitates materials capable of ultrafast (sub-picosecond) SF and the generation of long-lived (> microsecond) triplet excitons, a synthetic challenge. Some photosynthetic organisms have evolved sophisticated molecular architectures that demonstrate these criteria, but despite 40 years of study, the underlying SF mechanisms and its functional significance in these organisms remain unclear. Here, we use a suite of ultrafast and magneto-optical spectroscopic techniques to understand the mechanism of SF within light-harvesting 1 (LH1) complexes from wild-type and genetically modified photosynthetic bacteria. Our findings reveal a SF process, termed \"heterofission\", wherein singlet excitons are transformed into triplet excitons localised on adjacent carotenoid (Crt) and bacteriochlorophyll (BChl) molecules. We also uncover an unexpected functional role for SF in augmenting Crt-to-BChl photosynthetic energy transfer efficiency. By transiently storing electronic excitation within the SF-generated triplet pair, the system circumvents rapid thermalisation of Crt excitations, thereby enhancing energy transfer efficiency to the BChl Qy state, and enabling the organism to usefully harvest more sunlight.