School of Chemistry - Research Publications

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    A framework for multiexcitonic logic
    Hudson, RJ ; Macdonald, TSC ; Cole, JH ; Schmidt, TW ; Smith, TA ; McCamey, DR (NATURE PORTFOLIO, 2024-02)
    Exciton science sits at the intersection of chemical, optical and spin-based implementations of information processing, but using excitons to conduct logical operations remains relatively unexplored. Excitons encoding information could be read optically (photoexcitation-photoemission) or electrically (charge recombination-separation), travel through materials via exciton energy transfer, and interact with one another in stimuli-responsive molecular excitonic devices. Excitonic logic offers the potential to mediate electrical, optical and chemical information. Additionally, high-spin triplet and quintet (multi)excitons offer access to well defined spin states of relevance to magnetic field effects, classical spintronics and spin-based quantum information science. In this Roadmap, we propose a framework for developing excitonic computing based on singlet fission (SF) and triplet-triplet annihilation (TTA). Various molecular components capable of modulating SF/TTA for logical operations are suggested, including molecular photo-switching and multi-colour photoexcitation. We then outline a pathway for constructing excitonic logic devices, considering aspects of circuit assembly, logical operation synchronization, and exciton transport and amplification. Promising future directions and challenges are identified, and the potential for realizing excitonic computing in the near future is discussed.
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    The Multiple Roles of Na Ions in Highly Efficient CZTSSe Solar Cells
    Yang, W ; Ji, Y ; Chen, W ; Pan, Y ; Chen, Z ; Wu, S ; Russo, SP ; Xu, Y ; Smith, TA ; Chesman, A ; Mulvaney, P ; Liu, F (WILEY-V C H VERLAG GMBH, 2024-02-11)
    Sodium (Na) doping is a well-established technique employed in chalcopyrite and kesterite solar cells. While various improvements can be achieved in crystalline quality, electrical properties, or defect passivation of the absorber materials by incorporating Na, a comprehensive demonstration of the desired Na distribution in CZTSSe is still lacking. Herein, a straightforward Na doping approach by dissolving NaCl into the CZTS precursor solution is proposed. It is demonstrated that a favorable Na ion distribution should comprise a precisely controlled Na+ concentration at the front surface and an enhanced distribution within the bottom region of the absorber layer. These findings demonstrated that Na ions play several positive roles within the device, leading to an overall power conversion efficiency of 12.51%.
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    Selenium Nanoparticles as Potential Drug-Delivery Systems for the Treatment of Parkinson's Disease
    Kalcec, N ; Peranic, N ; Mamic, I ; Beus, M ; Hall, CR ; Smith, TA ; Sani, MA ; Turcic, P ; Separovic, F ; Vrcek, IV (AMER CHEMICAL SOC, 2023-09-20)
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    Charge Transfer-Mediated Multi-exciton Mechanisms in Weakly Coupled Perylene Dimers
    Manian, A ; Campaioli, F ; Hudson, RJ ; Cole, JH ; Schmidt, TW ; Lyskov, I ; Smith, TA ; Russo, SP (AMER CHEMICAL SOC, 2023-08-21)
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    An ITO-Free Kesterite Solar Cell
    Ji, Y ; Chen, W ; Yan, D ; Bullock, J ; Xu, Y ; Su, Z ; Yang, W ; Laird, JS ; Zheng, T ; Wu, N ; Zha, W ; Luo, Q ; Ma, C-Q ; Smith, TA ; Liu, F ; Mulvaney, P (WILEY-V C H VERLAG GMBH, 2024-02)
    Photovoltaic thin film solar cells based on kesterite Cu2 ZnSn(S, Se)4 (CZTSSe) have reached 13.8% sunlight-to-electricity conversion efficiency. However, this efficiency is still far from the Shockley-Queisser radiative limit and is hindered by the significant deficit in open circuit voltage (VOC ). The presence of high-density interface states between the absorber layer and buffer or window layer leads to the recombination of photogenerated carriers, thereby reducing effective carrier collection. To tackle this issue, a new window structure ZnO/AgNW/ZnO/AgNW (ZAZA) comprising layers of ZnO and silver nanowires (AgNWs) is proposed. This structure offers a simple and low-damage processing method, resulting in improved optoelectronic properties and junction quality. The ZAZA-based devices exhibit enhanced VOC due to the higher built-in voltage (Vbi ) and reduced interface recombination compared to the usual indium tin oxide (ITO) based structures. Additionally, improved carrier collection is demonstrated as a result of the shortened collection paths and the more uniform carrier lifetime distribution. These advances enable the fabrication of the first ITO-free CZTSSe solar cells with over 10% efficiency without an anti-reflective coating.
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    Quantifying the Relaxation Dynamics of Higher Electronic Excited States in Perylene.
    Hudson, RJ ; Manian, A ; Hall, CR ; Schmidt, TW ; Russo, SP ; Ghiggino, KP ; Smith, TA (American Chemical Society, 2023-08-31)
    Gating logical operations through high-lying electronic excited states presents opportunities for developing ultrafast, subnanometer computational devices. A lack of molecular systems with sufficiently long-lived higher excited states has hindered practical realization of such devices, but recent studies have reported intriguing photophysics from high-lying excited states of perylene. In this work, we use femtosecond spectroscopy supported by quantum chemical calculations to identify and quantify the relaxation dynamics of monomeric perylene's higher electronic excited states. The 21B2u state is accessed through single-photon absorption at 250 nm, while the optically dark 21Ag state is excited via the 11B3u state. Population of either state results in subpicosecond relaxation to the 11B3u state, and we quantify 21Ag and 21B2u state lifetimes of 340 and 530 fs, respectively. These lifetimes are significantly longer than the singlet fission time constant from the perylene 21B2u state, suggesting that the higher electronic states of perylene may be useful for gating logical operations.
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    A sandwich-like structural model revealed for quasi-2D perovskite films
    Zheng, F ; Hall, CR ; Angmo, D ; Zuo, C ; Rubanov, S ; Wen, Z ; Bradley, SJ ; Hao, X-T ; Gao, M ; Smith, TA ; Ghiggino, KP (Royal Society of Chemistry, 2021-04-28)
    The excellent performance and stability of perovskite solar cells (PSCs) based on quasi-2D Ruddlesden–Popper perovskites (RPPs) holds promise for their commercialization. Further improvement in the performance of 2D PSCs requires a detailed understanding of the microstructure of the quasi-2D perovskite films. Based on scanning transmission electron microscopy (STEM), time-resolved photoluminescence, and transient absorption measurements, a new sandwich-like structural model is proposed to describe the phase distribution of RPPs. In contrast to the conventional gradient distribution, it is found that small-n RPPs are sandwiched between large-n RPP phase layers at the front and back sides owing to crystallization initiated from both interfaces during film formation. This sandwich-like distribution profile facilitates excitons funneling from the film interior to both surfaces for dissociation while free carriers transport via large-n channels that permeate the film to ensure efficient charge collection by the corresponding electrodes, which is favorable for high-performance photovoltaics. This discovery provides a new fundamental understanding of the operating principles of 2D PSCs and has valuable implications for the design and optimization strategies of optoelectronic devices based on quasi-2D RPPs films.
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    Brownian Tree‐Shaped Dendrites in Quasi‐2D Perovskite Films and Their Impact on Photovoltaic Performance
    Zheng, F ; Angmo, D ; Hall, CR ; Rubanov, S ; Yuan, F ; Laird, JS ; Gao, M ; Smith, TA ; Ghiggino, KP (Wiley, 2022-05)
    Quasi-2D Ruddlesden–Popper perovskites (RPPs) are candidates for constructing perovskite solar cells (PSCs) with superior stability due to their tolerance to the external environment. Fully understanding the film growth mechanism and structure is crucial to further improve the performance of 2D-PSCs while maintaining device stability. In this work, the origin of Brownian tree-shaped dendrites formed in hot-cast methylammonium chloride (MACl)-doped BA2MAn−1PbnI3n+1 ( = 5) quasi-2D perovskite films are reported. Investigations based on optical, electronic, atomic force, and fluorescence microscopies reveal that the dendrites are assembled from large-n RPPs-dominated grains, while the nondendritic film area is composed of small-n RPPs grains and associated with film surface pits caused by the evaporation of MACl. It is proposed that these dendrites are grown by the diffusion-limited aggregation of the MA-rich intermediate phase domains that initially crystallize from the precursor. The formation of these dendrites in quasi-2D perovskite films upon MACl doping is accompanied by improved organization and crystallinity of the 2D RPPs, which benefits the photovoltaic performance. This work provides new insights into the formation mechanism of quasi-2D perovskite films that should assist device engineering strategies to further improve the performance of 2D PSCs.
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    An investigation of evanescent wave-induced fluorescence spectroscopy for exploring high refractive index media
    Chakraborty, S ; Xu, Y ; Roberts, A ; Goswami, D ; Smith, TA (IOP Publishing Ltd, 2023-01-01)
    Abstract Evanescent wave-induced fluorescence spectroscopy (EWIFS) is a widely used technique for probing the interfacial behavior of different complex media in investigations of samples in the physical, chemical, and biological sciences. This technique takes advantage of the sharply decaying evanescent field, established following total internal reflection (TIR) at the interface of two media, for spatially identifying the photoluminescence characteristics of the sample. The generation of the evanescent field requires the refractive index of the second medium to be lower than that of the first, so a major disadvantage of this increasingly widely used spectroscopic technique is the inability to exploit the advantages of EWIFS to image a sample with a higher refractive index than the incident substrate medium. A proposed configuration in which a thin, low refractive index intermediate layer is established between the TIR substrate and a high refractive index sample is investigated. We illustrate that this arrangement does not afford the desired advantages of evanescent field-induced fluorescence measurements for investigating high refractive index media.
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    Damage of amino acids by aliphatic peroxyl radicals: a kinetic and computational study
    Nathanael, JGG ; Yuan, B ; Hall, CRR ; Smith, TAA ; Wille, U (ROYAL SOC CHEMISTRY, 2023-03-15)
    Absolute second-order rate coefficients for the reaction of the N- and C-protected amino acids tyrosine (Tyr), tryptophan (Trp), methionine (Met) and proline (Pro) with triethylamine-derived aliphatic peroxyl radical TEAOO˙, which was used as a model for lipid peroxyl radicals, were determined using laser flash photolysis. For Ac-Tyr-OMe a rate coefficient of 1.4 × 104 M-1 s-1 was obtained, whereas the reactions with Ac-Trp-OMe and Ac-Met-OMe were slower by a factor of 4 and 6, respectively. For the reaction with Ac-Pro-OMe only an upper value of 103 M-1 s-1 could be determined, suggesting that Pro residues are not effective traps for lipid peroxyl radicals. Density functional theory (DFT) calculations revealed that the reactions proceed via radical hydrogen atom transfer (HAT) from the Cα position, indicating that the rate is determined by the exothermicity of the reaction. In the case of Ac-Tyr-OMe, HAT from the phenolic OH group is the kinetically preferred pathway, which shuts down when hydrogen bonding with an amine occurs. In an alkaline environment, where the phenolic OH group is deprotonated, the reaction is predicted to occur preferably at Cβ, likely through a proton-coupled electron transfer (PCET) mechanism.