Enhanced Photocatalytic and Photovoltaic Performance Arising from Unconventionally Low Donor-Y6 Ratios.

Development of both organic photovoltaics (OPVs) and organic photocatalysts has focused on utilizing the bulk heterojunction (BHJ). The BHJ promotes charge separation and enhances the carrier lifetime, but may give rise to increased charge traps, hindering performance. Here, high photocatalytic and photovoltaic performance is displayed by electron donor-acceptor (D-A) nanoparticles (NPs) and films, using the nonfullerene acceptor Y6 and polymer donor PIDT-T8BT. In contrast to conventional D-A systems, the charge generation in PIDT-T8BT:Y6 NPs is mainly driven by Y6, allowing a high performance even at a low D:A mass ratio of 1:50. The high performance at the low mass ratio is attributed to the amorphous behavior of PIDT-T8BT. Low ratios are generally thought to yield lower efficiency than the more conventional ≈1:1 ratio. However, the OPVs exhibit peak performance at a D:A ratio of 1:5. Similarly the NPs used for photocatalytic hydrogen evolution show peak performance at the 1:6.7 D:A ratio. Interestingly, for the PIDT-T8BT:Y6 system, as the polymer proportion increases, a reduced photocatalytic and photovoltaic performance is observed. The unconventional D:A ratios provide lower recombination losses and increased charge-carrier lifetime with undisrupted ambipolar charge transport in bulk Y6, enabling better performance than conventional ratios. This work reports novel light-harvesting materials in which performance is reduced due to unfavorable morphology as D:A ratios move toward conventional ratios of 1:1.2-1:1.

Atomic-Scale Characterization of Planar Selective-Area-Grown InAs/InGaAs Nanowires.

Atomic-scale information about the structural and compositional properties of novel semiconductor nanowires is essential to tailoring their properties for specific applications, but characterization at this length scale remains a challenging task. Here, quasi-1D InAs/InGaAs semiconductor nanowire arrays were grown by selective area epitaxy (SAE) using molecular beam epitaxy (MBE), and their subsequent properties were analyzed by a combination of atom probe tomography (APT) and aberration-corrected transmission electron microscopy (TEM). Results revealed the chemical composition of the outermost thin InAs layer, a fine variation in the indium content at the InAs/InGaAs interface, and lightly incorporated element tracing. The results highlight the importance of correlative microscopy approaches in revealing complex nanoscale structures, with TEM being uniquely suited to interrogating the crystallography of InGaAs NWs, whereas APT is capable of three-dimensional (3D) elemental mapping, revealing the subtle compositional variation near the boundary region. This work demonstrates a detailed pathway for the nanoscale structural assessment of novel one-dimensional (1D) nanomaterials.

Flexible Polymer X-ray Detectors with Non-fullerene Acceptors for Enhanced Stability: Toward Printable Tissue Equivalent Devices for Medical Applications.

There is growing interest in the development of novel materials and devices capable of ionizing radiation detection for medical applications. Organic semiconductors are promising candidates to meet the demands of modern detectors, such as low manufacturing costs, mechanical flexibility, and a response to radiation equivalent to human tissue. However, organic semiconductors have typically been employed in applications that convert low energy photons into high current densities, for example, solar cells and LEDs, and thus existing design rules must be re-explored for ionizing radiation detection where high energy photons are converted into typically much lower current densities. In this work, we report the optoelectronic and X-ray dosimetric response of a tissue equivalent organic photodetector fabricated with solution-based inks prepared from polymer donor poly(3-hexylthiophene) (P3HT) blended with either a non-fullerene acceptor (5Z,5'Z)-5,5'-((7,7'-(4,4,9,9-tetraoctyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(benzo[c][1,2,5]thiadiazole-7,4-diyl))bis(methanylylidene))bis(3-ethyl-2-thioxothiazolidin-4-one) (o-IDTBR) or a fullerene acceptor, [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Indirect detection of X-rays was achieved via coupling of organic photodiodes with a plastic scintillator. Both detectors displayed an excellent response linearity with dose, with sensitivities to 6 MV photons of 263.4 ± 0.6 and 114.2 ± 0.7 pC/cGy recorded for P3HT:PCBM and P3HT:o-IDTBR detectors, respectively. Both detectors also exhibited a fast temporal response, able to resolve individual 3.6 µs pulses from the linear accelerator. Energy dependence measurements highlighted that the photodetectors were highly tissue equivalent, though an under-response in devices compared to water by up to a factor of 2.3 was found for photon energies of 30-200 keV due to the response of the plastic scintillator. The P3HT:o-IDTBR device exhibited a higher stability to radiation, showing just an 18.4% reduction in performance when exposed to radiation doses of up to 10 kGy. The reported devices provide a successful demonstration of stable, printable, flexible, and tissue-equivalent radiation detectors with energy dependence similar to other scintillator-based detectors used in radiotherapy.

Atom probe specimen preparation methods for nanoparticles.

Revealing the position of materials with chemical selectivity at atomic scale within functional nanoparticles is essential to understand and control their performance and cutting-edge atom probe tomography is a powerful tool to undertake this task. In this paper, we demonstrate three effective methods to prepare the needle-shaped specimens required for atom probe tomography measurements from nanoparticles of different sizes and provide examples of how atom probe can be used to provide data that is critical to their functionality. Samples measured include lithium-ion batteries (LIBs) cathode nanoparticles (300 - 500 nm), nickel-doped silicon dioxide (Ni@SiO2) catalytic nanoparticles (100 - 200 nm) and tin-doped copper (Sn@Cu) catalytic nanoparticles (<100 nm). The methods presented can be used to address the ongoing challenge of specimen preparation from particle samples for atom probe measurement, and they provide high quality data. These methods will broaden the application of atom probe tomography and will provide alternative option for researchers to assess the performance/structure of their functional nanomaterials.

Towards high spatial resolution tissue-equivalent dosimetry for microbeam radiation therapy using organic semiconductors.

Spatially fractionated ultra-high-dose-rate beams used during microbeam radiation therapy (MRT) have been shown to increase the differential response between normal and tumour tissue. Quality assurance of MRT requires a dosimeter that possesses tissue equivalence, high radiation tolerance and spatial resolution. This is currently an unsolved challenge. This work explored the use of a 500 nm thick organic semiconductor for MRT dosimetry on the Imaging and Medical Beamline at the Australian Synchrotron. Three beam filters were used to irradiate the device with peak energies of 48, 76 and 88 keV with respective dose rates of 3668, 500 and 209 Gy s-1. The response of the device stabilized to 30% efficiency after an irradiation dose of 30 kGy, with a 0.5% variation at doses of 35 kGy and higher. The calibration factor after pre-irradiation was determined to be 1.02 ±â€…0.005 µGy per count across all three X-ray energy spectra, demonstrating the unique advantage of using tissue-equivalent materials for dosimetry. The percentage depth dose curve was within ±5% of the PTW microDiamond detector. The broad beam was fractionated into 50 microbeams (50 µm FHWM and 400 µm centre-to-centre distance). For each beam filter, the FWHMs of all 50 microbeams were measured to be 51 ±â€…1.4, 53 ±â€…1.4 and 69 ±â€…1.9 µm, for the highest to lowest dose rate, respectively. The variation in response suggested the photodetector possessed dose-rate dependence. However, its ability to reconstruct the microbeam profile was affected by the presence of additional dose peaks adjacent to the one generated by the X-ray microbeam. Geant4 simulations proved that the additional peaks were due to optical photons generated in the barrier film coupled to the sensitive volume. The simulations also confirmed that the amplitude of the additional peak in comparison with the microbeam decreased for spectra with lower peak energies, as observed in the experimental data. The material packaging can be optimized during fabrication by solution processing onto a flexible substrate with a non-fluorescent barrier film. With these improvements, organic photodetectors show promising prospects as a cost-effective high spatial resolution tissue-equivalent flexible dosimeter for synchrotron radiation fields.

Controlling Nanostructure in Inkjet Printed Organic Transistors for Pressure Sensing Applications.

This work reports the development of a highly sensitive pressure detector prepared by inkjet printing of electroactive organic semiconducting materials. The pressure sensing is achieved by incorporating a quantum tunnelling composite material composed of graphite nanoparticles in a rubber matrix into the multilayer nanostructure of a printed organic thin film transistor. This printed device was able to convert shock wave inputs rapidly and reproducibly into an inherently amplified electronic output signal. Variation of the organic ink material, solvents, and printing speeds were shown to modulate the multilayer nanostructure of the organic semiconducting and dielectric layers, enabling tuneable optimisation of the transistor response. The optimised printed device exhibits rapid switching from a non-conductive to a conductive state upon application of low pressures whilst operating at very low source-drain voltages (0-5 V), a feature that is often required in applications sensitive to stray electromagnetic signals but is not provided by conventional inorganic transistors and switches. The printed sensor also operates without the need for any gate voltage bias, further reducing the electronics required for operation. The printable low-voltage sensing and signalling system offers a route to simple low-cost assemblies for secure detection of stimuli in highly energetic systems including combustible or chemically sensitive materials.

Advanced Control of Drug Delivery for In Vivo Health Applications via Highly Biocompatible Self-Assembled Organic Nanoparticles.

The use of nanostructured materials for targeted and controlled delivery of bioactive molecules is an attractive alternative to conventional drug administration protocols, enabling selective targeting of diseased cells, lower administered dosages, and reduced systemic side effects. Although a variety of nanocarriers have been investigated in recent years, electroactive organic polymer nanoparticles present several exciting advantages. Here we demonstrate that thin films created from nanoparticles synthesized from violanthrone-79, an n-type semiconducting organic material, can incorporate and release dexamethasone in vitro in a highly controlled manner. By systematically altering the nanoparticle formation chemistry, we successfully tailored the size of the nanoparticles between 30 and 145 nm to control the initial amount of drug loaded into the organic particles. The biocompatibility of the different particles was tested using live/dead assays of dorsal root ganglion neurons isolated and cultured from mice, revealing that elevated levels of the sodium dodecyl sulfate surfactant used to create the smaller nanoparticles are cytotoxic; however, cell survival rates in nanoparticles larger than 45 nm exceed 86% and promote neurite growth and elongation. By manipulating the electrical stimulus applied to the electroactive nanoparticle films, we show an accelerated rate of drug release in comparison to passive release in aqueous media. Furthermore, pulsing the electrical stimulus was successfully used to selectively switch the accelerated release rate on and off. By combining the tuning of drug loading (through tailored nanoparticle synthesis) and drug release rate (through electrical stimulus protocols), we demonstrate a highly advanced control of drug delivery dosage in a biocompatible delivery vehicle. This work highlights the significant potential of electroactive organic nanoparticles for implantable devices that can deliver corticosteroids directly to the nervous system for the treatment of inflammation associated with neurological disorders, presenting a translatable pathway toward precision nanomedicine approaches for other drugs and diseases.

Remote Learning Facilitated by MyScope Explore.

In response to the requirements imposed by the COVID-19 pandemic in 2020, we developed a remote learning undergraduate workshop for 44 students at the University of Newcastle by embedding scanning electron microscope (SEM) images of Maratus (Peacock) spiders into the MyScope Explore environment. The workshop session had two main components: 1) to use the online MyScope Explore tool to virtually image scales with structural color and pigmented color on Maratus spiders; 2) to join a live SEM session via Zoom to image an actual Maratus spider. In previous years, the undergraduate university students attending this annual workshop would enter the Microscopy Facility at the University of Newcastle to image specimens with SEM; however, in 2020 the Microscopy Facility was closed to student visitors, and this virtual activity was developed in order to proceed with the educational event. The program was highly successful and constitutes a platform that can be used in the future by universities for teaching microscopy remotely.

Characterization of an organic semiconductor diode for dosimetry in radiotherapy.

PURPOSE: The development of novel detectors for dosimetry in advanced radiotherapy modalities requires materials that have a water equivalent response to ionizing radiation such that characterization of radiation beams can be performed without the need for complex calibration procedures and correction factors. Organic semiconductors are potentially an ideal technology in fabricating devices for dosimetry due to tissue equivalence, mechanical flexibility, and relatively cheap manufacturing cost. The response of a commercial organic photodetector (OPD), coupled to a plastic scintillator, to ionizing radiation from a linear accelerator and orthovoltage x-ray tube has been characterized to assess its potential as a dosimeter for radiotherapy. The radiation hardness of the OPD has also been investigated to demonstrate its longevity for such applications. METHODS: Radiation hardness measurements were achieved by observing the response of the OPD to the visible spectrum and 70 keV x rays after pre-exposure to 40 kGy of ionizing radiation. The response of a preirradiated OPD to 6-MV photons from a linear accelerator in reference conditions was compared to a nonirradiated OPD with respect to direct and indirect (RP400 plastic scintillator) detection mechanisms. Dose rate dependence of the OPD was measured by varying the surface-to-source distance between 90 and 300 cm. Energy dependence was characterized from 29.5 to 129 keV with an x-ray tube. The percentage depth dose (PDD) curves were measured from 0.5 to 20 cm and compared to an ionization chamber. RESULTS: The OPD sensitivity to visible light showed substantial degradation of the broad 450 to 600 nm peak from the donor after irradiation to 40 kGy. After irradiation, the spectral shape has a dominant absorbance peak at 370 nm, as the acceptor better withstood radiation damage. Its response to x rays stabilized to 30% after 35 kGy, with a 0.5% difference between 770 Gy increments. The OPD exhibited reproducible detection of ionizing radiation when coupled with a scintillator. Indirect detection showed a linear response from 25 to 500 cGy and constant response to dose rates from 0.31 Gy/pulse to 3.4 × 10-4  Gy/pulse. However, without the scintillator, response increased by 100% at low dose rates. Energy independence between 100 keV and 1.2 MeV advocates their use as a dosimeter without beam correction factors. A dependence on the scintillator thickness used during a comparison of the PDD to the ionizing chamber was identified. A 1-mm-thick scintillator coupled with the OPD demonstrated the best agreement of ± 3%. CONCLUSIONS: The response of OPDs to ionizing radiation has been characterized, showing promising use as a dosimeter when coupled with a plastic scintillator. The mechanisms of charge transport and trapping within organic materials varies for visible and ionizing radiation, due to differing properties for direct and indirect detection mechanisms and observing a substantial decrease in sensitivity to the visible spectrum after 40 kGy. This study proved that OPDs produce a stable response to 6-MV photons, and with a deeper understanding of the charge transport mechanisms due to exposure to ionizing radiation, they are promising candidates as the first flexible, water equivalent, real-time dosimeter.

Characterization of a plastic dosimeter based on organic semiconductor photodiodes and scintillator.

BACKGROUND AND PURPOSE: Measurement of dose delivery is essential to guarantee the safety of patients undergoing medical radiation imaging or treatment procedures. This study aimed to evaluate the ability of organic semiconductors, coupled with a plastic scintillator, to measure photon dose in clinically relevant conditions, and establish its radiation hardness. Thereby, proving organic devices are capable of being a water-equivalent, mechanically flexible, real-time dosimeter. MATERIALS AND METHODS: The shelf-life of an organic photodiode was analyzed to 40 kGy by comparison of the charge-collection-efficiency of a 520 nm light emitting diode. A non-irradiated and pre-irradiated photodiode was coupled to a plastic scintillator and their response to 6 MV photons was investigated. The dose linearity, dose-per-pulse dependence and energy dependence was characterized. Finally, the percentage depth dose (PDD) between 0.5 and 20 cm was compared with ionization chamber measurements. RESULTS: Sensitivity to 6 MV photons was (190 ± 0.28) pC/cGy and (170 ± 0.11) pC/cGy for the non-irradiated and pre-irradiated photodiode biased at -2 V. The response was independent of the dose-per-pulse between 0.031 and 0.34 mGy/pulse. An energy dependence was found for low keV energies, explained by the energy dependence of the scintillator which plateaued between 70 keV and 1.2 MeV. The PDD was within ±3% of the ionization chamber. CONCLUSION: Coupling an organic photodiode with a plastic scintillator provided reliable measurement of a range of photon energies. Dose-per-pulse and energy independence advocate their use as a dosimeter, specifically image-guided treatment without beam-quality correction factors. Degradation effects of organic semiconducting materials deteriorate sensor response but can be stabilized.

Manipulating nanoscale structure to control functionality in printed organic photovoltaic, transistor and bioelectronic devices.

Printed electronics is simultaneously one of the most intensely studied emerging research areas in science and technology and one of the fastest growing commercial markets in the world today. For the past decade the potential for organic electronic (OE) materials to revolutionize this printed electronics space has been widely promoted. Such conviction in the potential of these carbon-based semiconducting materials arises from their ability to be dissolved in solution, and thus the exciting possibility of simply printing a range of multifunctional devices onto flexible substrates at high speeds for very low cost using standard roll-to-roll printing techniques. However, the transition from promising laboratory innovations to large scale prototypes requires precise control of nanoscale material and device structure across large areas during printing fabrication. Maintaining this nanoscale material control during printing presents a significant new challenge that demands the coupling of OE materials and devices with clever nanoscience fabrication approaches that are adapted to the limited thermodynamic levers available. In this review we present an update on the strategies and capabilities that are required in order to manipulate the nanoscale structure of large area printed organic photovoltaic (OPV), transistor and bioelectronics devices in order to control their device functionality. This discussion covers a range of efforts to manipulate the electroactive ink materials and their nanostructured assembly into devices, and also device processing strategies to tune the nanoscale material properties and assembly routes through printing fabrication. The review finishes by highlighting progress in printed OE devices that provide a feedback loop between laboratory nanoscience innovations and their feasibility in adapting to large scale printing fabrication. The ability to control material properties on the nanoscale whilst simultaneously printing functional devices on the square metre scale is prompting innovative developments in the targeted nanoscience required for OPV, transistor and biofunctional devices.

Role of Stabilizing Surfactants on Capacitance, Charge, and Ion Transport in Organic Nanoparticle-Based Electronic Devices.

Deposition of functionalized nanoparticles onto solid surfaces has created a new revolution in electronic devices. Surface adsorbates such as ionic surfactants or additives are often used to stabilize such nanoparticle suspensions; however, little is presently known about the influence of such surfactants and additives on specific electronic and chemical functionality of nanoparticulate electronic devices. This work combines experimental measurements and theoretical models to probe the role of an ionic surfactant in the fundamental physical chemistry and electronic charge carrier behavior of photodiode devices prepared using multicomponent organic electronic nanoparticles. A large capacitance was detected, which could be subsequently manipulated using the external stimuli of light, temperature, and electric fields. It was demonstrated that analyzing this capacitance through the framework of classical semiconductor analysis produced substantially misleading information on the electronic trap density of the nanoparticles. Electrochemical impedance measurements demonstrated that it is actually the stabilizing surfactant that creates capacitance through two distinct mechanisms, each of which influenced charge carrier behavior differently. The first mechanism involved a dipole layer created at the contact interfaces by mobile ions, a mechanism that could be replicated by addition of ions to solution-cast devices and was shown to be the major origin of restricted electronic performance. The second mechanism consisted of immobile ionic shells around individual nanoparticles and was shown to have a minor impact on device performance as it could be removed upon addition of electronic charge in the photodiodes through either illumination or external bias. The results confirmed that the surfactant ions do not create a significantly increased level of charge carrier traps as has been previously suspected, but rather, preventing the diffusion of mobile ions through the nanoparticulate film and their accumulation at contacts is critical to optimize the performance.

Building intermixed donor-acceptor architectures for water-processable organic photovoltaics.

A modified synthesis method for aqueous nanoparticle printing inks, based upon vacuum-assisted solvent removal, is reported. Poly(3-hexylthiophene):phenyl C61 butyric acid methyl ester nanoparticle inks were prepared via this modified miniemulsion method, leading to both an improvement in photoactive layer morphology and a substantial reduction in the ink fabrication time. A combination of UV-visible spectroscopy, photoluminescence spectroscopy and scanning transmission X-ray microscopy measurements revealed a nanoparticle morphology comprising highly intermixed donor-acceptor domains. Consistent with these measurements, dynamic mechanical thermal analysis of the nanoparticles showed a glass transition temperature (Tg) of 104 °C, rather than a pure polymer phase or pure fullerene phase Tg. Together the spectroscopy, microscopy and thermomechanical data indicate that rapid solvent removal generates a more blended nanoparticle morphology. As such, this study highlights a new experimental lever for optimising nanostructure in the photoactive layer of nanoparticulate organic photovoltaic devices by enabling highly intermixed donor-acceptor architectures to be built from customised nanoparticulate inks.

Roll-to-roll solvent annealing of printed P3HT : ICXA devices.

Currently, large-scale roll-to-roll production of printed organic photovoltaics (OPVs) involves high temperature annealing steps that are not compatible with thermally sensitive substrates, such as coated fabrics. In particular, the processing temperatures needed to produce the required crystalline ordering in the printed films are typically above the deformation and melting-points of these substrates. In this paper we investigate the use of local solvent recrystallisation (solvent annealing) on the roll-to-roll scale as a method for avoiding high-temperature thermal annealing. Solvent annealing was performed by slot-die coating a mixture of chloroform and methanol over a previously printed P3HT ICXA active layer film. Peak device performance was found for the 30% chloroform/70% methanol annealing case which increased device performance by a factor of 4 over the not treated devices.

Optimisation of purification techniques for the preparation of large-volume aqueous solar nanoparticle inks for organic photovoltaics.

In this study we have optimised the preparation conditions for large-volume nanoparticle inks, based on poly(3-hexylthiophene) (P3HT):indene-C60 multiadducts (ICxA), through two purification processes: centrifugal and crossflow ultrafiltration. The impact of purification is twofold: firstly, removal of excess sodium dodecyl sulfate (SDS) surfactant from the ink and, secondly, concentration of the photoactive components in the ink. The removal of SDS was studied in detail both by a UV-vis spectroscopy-based method and by surface tension measurements of the nanoparticle ink filtrate; revealing that centrifugal ultrafiltration removed SDS at a higher rate than crossflow ultrafiltration even though a similar filter was applied in both cases (10,000 Da Mw cut-off). The influence of SDS concentration on the aqueous solar nanoparticle (ASNP) inks was investigated by monitoring the surface morphology/topography of the ASNP films using atomic force microscopy (AFM) and scanning electron microscopy (SEM) and photovoltaic device performance as a function of ultrafiltration (decreasing SDS content). The surface morphology/topography showed, as expected, a decreased number of SDS crystallites on the surface of the ASNP film with increased ultrafiltration steps. The device performance revealed distinct peaks in efficiency with ultrafiltration: centrifuge purified inks reached a maximum efficiency at a dilution factor of 7.8 × 104, while crossflow purified inks did not reach a maximum efficiency until a dilution factor of 6.1 × 109. This difference was ascribed to the different wetting properties of the prepared inks and was further corroborated by surface tension measurements of the ASNP inks which revealed that the peak efficiencies for both methods occurred for similar surface tension values of 48.1 and 48.8 mN m-1. This work demonstrates that addressing the surface tension of large-volume ASNP inks is key to the reproducible fabrication of nanoparticle photovoltaic devices.

Activation of Organic Photovoltaic Light Detectors Using Bend Leakage from Optical Fibers.

This work investigates the detection and subsequent utilization of leaked light from bends in a silica optical fiber using organic photovoltaic detectors. The optic power lost by single mode and multimode silica optical fibers was calibrated for bend radii between 1 and 7 mm for 532 and 633 nm light, exhibiting excellent agreement with previous theoretical solutions. The spatial location of maximum power leakage on the exterior of the fiber was found to exist in the same plane as the fiber, with a 10° offset from the normal. Two different organic photovoltaic detectors fabricated using a poly(3-hexylthiophene):indene-C60-bisadduct donor-acceptor blend cast from chloroform and chlorobenzene were fabricated to detect the leaked light. The two detectors exhibited different photovoltaic performances, predominantly due to different active layer thicknesses. Both devices showed sensitivity to leakage light, exhibiting voltages between 200 and 300 mV in response to leaked light from the fiber. The temporal responses of the devices were observed to differ, with a rise time from 10% to 90% of maximum voltage of 1430 µs for the chlorobenzene device, and a corresponding rise time of 490 µs for the higher performing chloroform device. The two OPVs were used to simultaneously detect leaked light from induced bends in the optical fiber, with the differing temporal profiles employed to create a unique time-correlated detection signal with enhanced security. The delay between detection of each OPV voltage could be systematically varied, allowing for either a programmable and secure single detection signal or triggering of multiple events with variable time resolution. The results reported in this study present exciting avenues toward the deployment of this simple and noninvasive optical detection system in a range of different applications.

Molecular engineering of zinc phthalocyanine sensitizers for efficient dye-sensitized solar cells.

Asymmetric zinc phthalocyanines with alkyl chain substituents formed highly efficient light-harvesting layers on a TiO2 surface. Dye-sensitized solar cells using PcS20 exhibited a record efficiency of 6.4% under one-sun irradiation.

A nonconjugated bridge in dimer-sensitized solar cells retards charge recombination without decreasing charge injection efficiency.

Dye sensitized solar cells (DSSCs) employing a dimer porphyrin, which was synthesised with two porphyrin units connected without conjugation, have shown that both porphyrin components can contribute to photocurrent generation, that is, more than 50 % internal quantum efficiency. In addition, the open-circuit voltage (Voc) of the DSSCs was higher than that of DSSCs using monomer porphyrins. In this paper, we first optimized cell structure and fabrication conditions. We obtained more than 80% incident photon to current conversion efficiency from the dimer porphyrin sensitized DSSCs and higher Voc and energy conversion efficiency than monomer porphyrin sensitized solar cells. To examine the origin of the higher Voc, we measured electron lifetime in the DSSCs with various conditions, and found that the dimer system increased the electron lifetime by improving the steric blocking effect of the dye layer, whilst the lack of a conjugated linker prevents an increase in the attractive force between conjugated sensitizers and the acceptor species in the electrolyte. The results support a hypothesis; dispersion force is one of the factors influencing the electron lifetime in DSSCs.

Molecular design rule of phthalocyanine dyes for highly efficient near-IR performance in dye-sensitized solar cells.

A series of zinc-phthalocyanine sensitizers (PcS16-18) with different adsorption sites have been designed and synthesized in order to investigate the dependence of adsorption-site structures on the solar-cell performances in zinc-phthalocyanine based dye-sensitized solar cells. The change of adsorption site affected the electron injection efficiency from the photoexcited dye into the nanocrystalline TiO2 semiconductor, as monitored by picosecond time-resolved fluorescence spectroscopy. The zinc-phthalocyanine sensitizer PcS18, possessing one carboxylic acid directly attached to the ZnPc ring and six 2,6-diisopropylphenoxy units, showed a record power conversion efficiency value of 5.9 % when used as a light-harvesting dye on a TiO2 electrode under one simulated solar condition.

Porphyrins for dye-sensitised solar cells: new insights into efficiency-determining electron transfer steps.

Porphyrin molecules offer immense potential as the light harvesting component of dye-sensitised nanocrystalline TiO(2) solar cells. Synthetic porphyrin dyes were amongst the first dyes trialled for sensitisation of inorganic semiconducting oxides. Today, they exhibit the best performance reported for dye-sensitised solar cells. Accompanying the significant performance improvement over the last two decades is a much improved understanding of efficiency-determining fundamental electron transfer steps, from charge photogeneration to recombination. In this feature article we highlight our recent discoveries of the influence of porphyrin molecule structure on efficiency determining electron transfer kinetics and device performance by systematically changing the molecular structure and observing electron injection and recombination kinetics using time-resolved optical and electrical probes. Despite our observation of ultrafast charge injection for all porphyrin dyes studied by transient absorption spectroscopy, the injection yield estimated using an internal standard remains below 100% and depends strongly on the molecular structure. The observed discrepancy between kinetic competition and the injection yield is attributed to non-injecting dyes, probably arising due to inhomogeneity. A very interesting sub-ns (0.5 ns to 100 ns) charge recombination channel between photo-injected electrons and porphyrin cations is observed, which is found to be more prominent in free-base porphyrin dyes with a conjugated linker. Charge recombination between the acceptor species in the redox containing electrolyte and injected electrons is shown to be an important limitation of most porphyrin-sensitised solar cells, accelerated by the presence of porphyrin molecules at the TiO(2)-electrolyte interface. This recombination reaction is strongly dependent on the porphyrin molecular structure. Bulky substituents, using a porphyrin dimer instead of a porphyrin monomer, a light soaking treatment of freshly prepared films and co-sensitization of TiO(2) with multiple dyes are shown to be successful strategies to improve electron lifetime. Finally, new developments unique to porphyrin dye-sensitised solar cells, including performance enhancements from a light exposure treatment of a zinc porphyrin dye, a significant performance improvement observed after co-sensitisation of TiO(2) with free-base and zinc porphyrin dyes and the use of porphyrin dimers with increased light harvesting in thin-film TiO(2) solar cells are described.