School of Chemistry - Research Publications
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ItemNo Preview AvailableAlkyl Chain Length-Dependent Amine-Induced Crystallization for Efficient Interface Passivation of Perovskite Solar Cells(WILEY, 2023-07)Abstract Efficient surface passivation of perovskite solar cells (PSC) using treatment with ammonium salts is demonstrated as an efficient method to enhance the device performance, owing to the affinity between the amine group and [PbI6]4− octahedron. However, due to their high solubility in polar solvents (DMF/DMSO), ammonium salts are more difficult to use in passivation of the interface between the electron transport layer and perovskite thin film in n‐i‐p structured PSCs. In this report, this work successfully links the amine group with a fullerene through a series of increasing carbon chain length, from two to twelve methylene units (FC‐X, X = 2, 6, 12), and then introduce the synthesized molecules as interface passivation layers into SnO2‐based planar n‐i‐p PSCs. Results show that the interface passivation effect is highly dependent on the side‐chain length, and the longer chain length amine‐functionalized fullerene is more beneficial for the device performance. A power conversion efficiency as high as 21.2% is achieved by using FC‐12. The surface energy, perovskite crystallite size and electron transfer capacity correlate with the linker chain length. This work develops an amine‐induced anchored crystallization of perovskite to unravel the mechanism of this passivation effect. As expected, enhanced device stability is also observed in the FC‐12 passivated PSCs.
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ItemPretty Cool Beetles: Can Manipulation of Visible and Near-Infrared Sunlight Prevent Overheating?(OXFORD UNIV PRESS, 2022-09-13)Passive thermoregulation is an important strategy to prevent overheating in thermally challenging environments. Can the diversity of optical properties found in Christmas beetles (Rutelinae) be an advantage to keep cool? We measured changes in temperature of the elytra of 26 species of Christmas beetles, exclusively due to direct radiation from a solar simulator in visible (VIS: 400-700 nm) and near infrared (NIR: 700-1700 nm) wavebands. Then, we evaluated if the optical properties of elytra could predict their steady state temperature and heating rates, while controlling for size. We found that higher absorptivity increases the heating rate and final steady state of the beetle elytra in a biologically significant range (3 to 5°C). There was substantial variation in the absorptivity of Christmas beetle elytra; and this variation was achieved by different combinations of reflectivity and transmissivity in both VIS and NIR. Size was an important factor predicting the change in temperature of the elytra after 5 min (steady state) but not maximum heating rate. Lastly, we show that the presence of the elytra covering the body of the beetle can reduce heating of the body itself. We propose that beetle elytra can act as a semi-insulating layer to enable passive thermoregulation through high reflectivity of elytra, resulting in low absorptivity of solar radiation. Alternatively, if beetle elytra absorb a high proportion of solar radiation, they may reduce heat transfer from the elytra to the body through behavioral or physiological mechanisms.
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ItemReduced Recombination in High Efficiency Molecular Nematic Liquid Crystalline: Fullerene Solar Cells(WILEY-V C H VERLAG GMBH, 2016-11-23)Bimolecular recombination in bulk heterojunction organic solar cells is the process by which nongeminate photogenerated free carriers encounter each other, and combine to form a charge transfer (CT) state which subsequently relaxes to the ground state. It is governed by the diffusion of the slower and faster carriers toward the electron donor–acceptor interface. In an increasing number of systems, the recombination rate constant is measured to be lower than that predicted by Langevin's model for relative Brownian motion and the capture of opposite charges. This study investigates the dynamics of charge generation, transport, and recombination in a nematic liquid crystalline donor:fullerene acceptor system that gives solar cells with initial power conversion efficiencies of >9.5%. Unusually, and advantageously from a manufacturing perspective, these efficiencies are maintained in junctions thicker than 300 nm. Despite finding imbalanced and moderate carrier mobilities in this blend, strongly suppressed bimolecular recombination is observed, which is ≈150 times less than predicted by Langevin theory, or indeed, more recent and advanced models that take into account the domain size and the spatial separation of electrons and holes. The suppressed bimolecular recombination arises from the fact that ground‐state decay of the CT state is significantly slower than dissociation.
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ItemPyridine End-Capped Polymer to Stabilize Organic Nanoparticle Dispersions for Solar Cell Fabrication through Reversible Pyridinium Salt Formation(AMER CHEMICAL SOC, 2021-08-04)Bulk-heterojunction nanoparticle dispersions in water or alcohol can be employed as eco-friendly inks for the fabrication of organic solar cells by printing or coating. However, one major drawback is the need for stabilizing surfactants, which facilitate nanoparticle formation but later hamper device performance. When surfactant-free dispersions are formulated, a strong limitation is imposed by the dispersion concentration due to the tendency of nanoparticles to aggregate. In this work, pyridine end-capped poly(3-hexylthiophene) (P3HT-Py) is synthesized and included as an additive for the stabilization of P3HT:indene-C60 bis-adduct (ICBA) nanoparticle dispersions. In the presence of acetic acid (AcOH), a surface-active pyridinium acetate end-capped P3HT ion pair, P3HT-PyH+AcO-, is formed which effectively stabilizes the dispersion and hence allows the formation of dispersions with smaller nanoparticle sizes and higher concentrations of up to 30 mg/mL in methanol. The dispersions exhibit an enhanced shelf-lifetime of at least 60 days at room temperature. After the deposition of light-harvesting layers from the nanoparticle dispersions, the ion-pair formation is reversed at elevated temperatures leading to regeneration of P3HT-Py and AcOH. The AcOH evaporates from the active layer, while the performance of the corresponding solar cells is not affected by the residual P3HT-Py in the devices. Enhanced nanoparticle stability is achieved with only 0.017 wt % pyridine in the P3HT/ICBA formulation.
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ItemNo Preview AvailableReduced Recombination and Capacitor-like Charge Buildup in an Organic Heterojunction(American Chemical Society, 2020-02-05)Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination—poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains—away from the interface—resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.
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ItemEnhancement of efficiency in organic photovoltaic devices containing self-complementary hydrogen-bonding domains(BEILSTEIN-INSTITUT, 2013-06-06)Self-complementary hydrogen-bonding domains were incorporated as the electron deficient unit in "push-pull", p-type small molecules for organic photovoltaic active layers. Such compounds were found to enhance the fill factor, compared with similar non-self-organized compounds reported in the literature, leading to higher device efficiencies. Evidence is presented that the ability of these molecules to form one-dimensional hydrogen-bonded chains and subsequently exhibit hierarchical self-assembly into nanostructured domains can be correlated with improved device efficiency.
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ItemControlled synthesis of poly(3-hexylthiophene) in continuous flow(BEILSTEIN-INSTITUT, 2013-07-25)There is an increasing demand for organic semiconducting materials with the emergence of organic electronic devices. In particular, large-area devices such as organic thin-film photovoltaics will require significant quantities of materials for device optimization, lifetime testing and commercialization. Sourcing large quantities of materials required for the optimization of large area devices is costly and often impossible to achieve. Continuous-flow synthesis enables straight-forward scale-up of materials compared to conventional batch reactions. In this study, poly(3-hexylthiophene), P3HT, was synthesized in a bench-top continuous-flow reactor. Precise control of the molecular weight was demonstrated for the first time in flow for conjugated polymers by accurate addition of catalyst to the monomer solution. The P3HT samples synthesized in flow showed comparable performance to commercial P3HT samples in bulk heterojunction solar cell devices.
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ItemBulk Heterojunction Nanomorphology of Fluorenyl Hexa-peri-hexabenzocoronene-Fullerene Blend Films(AMER CHEMICAL SOC, 2013-11-27)In this study, the nanomorphology of fluorenyl hexa-peri-hexabenzocoronene:[6,6]-phenyl C61-butyric acid methyl ester (FHBC:PC61BM) absorber layers of organic solar cells was investigated. Different electron microscopical techniques, atomic force microscopy, and grazing incidence wide-angle X-ray scattering were applied for a comprehensive nanomorphology analysis. The development of the nanomorphology upon sample annealing and the associated change of the device performance were investigated. It was shown that the annealing process enhances the phase separation and therefore the bulk heterojunction structure. Due to π-π stacking, the FHBC molecules assemble into columnar stacks, which are already present before annealing. While the nonannealed sample consists of a mixture of homogeneously distributed PC61BM molecules and FHBC stacks with a preferential in-plane stack orientation, crystalline FHBC precipitates occur in the annealed samples. These crystals, which consist of hexagonal arranged FHBC stacks, grow with increased annealing time. They are distributed homogeneously over the whole volume of the absorber layer as revealed by electron tomography. The FHBC stacks, whether in the two phase mixture or in the pure crystalline precipitates, exhibit an edge-on orientation, according to results from grazing incidence wide-angle X-ray scattering (GIWAXS), dark-field transmission electron microscopy (DF TEM) imaging and selective area electron diffraction (SAED). The best solar cell efficiencies were obtained after 20 or 40 s sample annealing. These annealing times induce an optimized degree of phase separation between donor and acceptor material.
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ItemBenzotriazole-based donor-acceptor conjugated polymers with a broad absorption in the visible range(ROYAL SOC CHEMISTRY, 2014-02-21)
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ItemThiazolyl substituted benzodithiophene copolymers: synthesis, properties and photovoltaic applications(Royal Society of Chemistry, 2014)Three new conjugated polymers based on 5-decylthiazol-2-yl substituted benzodithiophene have been synthesized by Stille cross-coupling polymerization. 1,3-Dibromo-5-octylthieno[3,4-c]pyrrole-4,6-dione (M1), 2,5-diethylhexyl-3,6-bis(5-bromothiophen-2-yl)pyrrolo[3,4-c]-pyrrole-1,4-dione (M2) and 4,6-dibromo-thieno[3,4-b]thiophene-2-dodecyl carboxylate (M3) were used as acceptor building blocks for the synthesis of conjugated donor-acceptor polymers. The thermal, optical, electrochemical, and photovoltaic properties of the synthesized polymers were studied.