Enhancing LED spectral output with perylene dye-based remote phosphor.

LEDs offer a wide range of spectral output with high efficiencies. However, the efficiencies of solid-state LEDs with green and yellow wavelengths are rather low due to the lack of suitable direct bandgap materials. Here, we introduce and develop perylene-enhanced green LEDs that produce a higher wall-plug efficiency of 48% compared to 38% for a solid-state green LED. While the wall-plug efficiency of the perylene-enhanced red LED is still lower than that of a solid-state red LED, we demonstrate that remote phosphor colour converters are effective solutions for targeted spectral tuning across the visible spectrum for horticultural lighting. In this work, we retrofit existing white LEDs and augment photosynthesis via spectral output tuning to achieve a higher red-to-blue ratio. Our results show a significant improvement in plant growth by up to 39%, after a 4-month growth cycle. We observe no visible degradation of the colour converter even under continuous illumination with a current of 400 mA. This opens up new opportunities for using perylene-based colour converters for tuneable illumination with high brightness.

Patterning at the Resolution Limit of Commercial Electron Beam Lithography.

It has been long known that low molecular weight resists can achieve a very high resolution, theoretically close to the probe diameter of the electron beam lithography (EBL) system. Despite technological improvements in EBL systems, the advances in resists have lagged behind. Here we demonstrate that a low-molecular-mass single-source precursor resist (based on cadmium(II) ethylxanthate complexed with pyridine) is capable of a achieving resolution (4 nm) that closely matches the measured probe diameter (∼3.8 nm). Energetic electrons enable the top-down radiolysis of the resist, while they provide the energy to construct the functional material from the bottom-up─unit cell by unit cell. Since this occurs only within the volume of resist exposed to primary electrons, the minimum size of the patterned features is close to the beam diameter. We speculate that angstrom-scale patterning of functional materials is possible with single-source precursor resists using an aberration-corrected electron beam writer with a spot size of ∼1 Å.

Surface band bending and carrier dynamics in colloidal quantum dot solids.

Band bending in colloidal quantum dot (CQD) solids has become important in driving charge carriers through devices. This is typically a result of band alignments at junctions in the device. Whether band bending is intrinsic to CQD solids, i.e. is band bending present at the surface-vacuum interface, has previously been unanswered. Here we use photoemission surface photovoltage measurements to show that depletion regions are present at the surface of n and p-type CQD solids with various ligand treatments (EDT, MPA, PbI2, MAI/PbI2). Using laser-pump photoemission-probe time-resolved measurements, we show that the timescale of carrier dynamics in the surface of CQD solids can vary over at least 6 orders of magnitude, with the fastest dynamics on the order of microseconds in PbS-MAI/PbI2 solids and on the order of seconds for PbS-MPA and PbS-PbI2. By investigating the surface chemistry of the solids, we find a correlation between the carrier dynamics timescales and the presence of oxygen contaminants, which we suggest are responsible for the slower dynamics due to deep trap formation.

Silicon Nanoantenna Mix Arrays for a Trifecta of Quantum Emitter Enhancements.

Dielectric nanostructures have demonstrated optical antenna effects due to Mie resonances. Previous work has exhibited enhancements in absorption, emission rates and directionality with practical limitations. In this paper, we present a Si mix antenna array to achieve a trifecta enhancement of ∼1200-fold with a Purcell factor of ∼47. The antenna design incorporates ∼10 nm gaps, within which fluorescent molecules strongly absorb the pump laser energy through a resonant mode. In the emission process, the antenna array increases the radiative decay rates of the fluorescence molecules via a Purcell effect and provides directional emission through a separate mode. This work could lead to novel CMOS-compatible platforms to enhance fluorescence for biological and chemical applications.

Influence of Multistep Surface Passivation on the Performance of PbS Colloidal Quantum Dot Solar Cells.

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multistep surface treatments, which combine two or more strategies, are important for creating films with high carrier mobility that are well passivated against trap states and oxidation. Here, we examine the effect of a number of these surface treatments on PbS CQD films, including cation exchange to form PbS/CdS core/shell CQDs, and solid-state ligand-exchange treatments with Cl, Br, I, and 1,2-ethanedithiol (EDT) ligands. Using laboratory-based and synchrotron-radiation-excited X-ray photoelectron spectroscopy (XPS), we examine the compositions of the surface layer before and after treatment, and correlate this with the performance data and stability in air. We find that halide ion treatments may etch the CQD surfaces, with detrimental effects on the air stability and solar cell device performance caused by a reduction in the proportion of passivated surface sites. We show that films made up of PbS/CdS CQDs are particularly prone to this, suggesting Cd is more easily etched from the surface than Pb. However, by choosing a less aggressive ligand treatment, a good coverage of passivators on the surface can be achieved. We show that halide anions bind preferentially to surface Pb (rather than Cd). By isolating the part of XPS signal originating from the topmost surface layer of the CQD, we show that air stability is correlated with the total number of passivating agents (halide + EDT + Cd) at the surface.

The passivating effect of cadmium in PbS/CdS colloidal quantum dots probed by nm-scale depth profiling.

Achieving control of the surface chemistry of colloidal quantum dots (CQDs) is essential to fully exploit their properties in solar cells, but direct measurement of the chemistry and electronic structure in the outermost atomic layers is challenging. Here we probe the surface oxidation and passivation of cation-exchanged PbS/CdS core/shell CQDs with sub nm-scale precision using synchrotron-radiation-excited depth-profiling photoemission. We investigate the surface composition of the topmost 1-2.5 nm of the CQDs as a function of depth, for CQDs of varying CdS shell thickness, and examine how the surface changes after prolonged air exposure. We demonstrate that the Cd is localized at the surface of the CQDs. The surface-localized products of oxidation are identified, and the extent of oxidation quantified. We show that oxidised sulfur species are progressively eliminated as Cd replaces Pb at the surface. A sub-monolayer surface 'decoration' of Cd is found to be effective in passivating the CQDs. We show that the measured energy-level alignments at PbS/CdS colloidal quantum dot surfaces differ from those expected on the basis of bulk band offsets, and are strongly affected by the oxidation products. We develop a model for the passivating action of Cd. The optimum shell thickness (of around 0.1 nm, previously found to give maximised power conversion efficiency in PbS/CdS solar cells) is found to correspond to a trade-off between the rate of oxidation and the introduction of a surface barrier to charge transport.

Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics.

The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation.

High Performance PbS Quantum Dot/Graphene Hybrid Solar Cell with Efficient Charge Extraction.

Hybrid colloidal quantum dot (CQD) solar cells are fabricated from multilayer stacks of lead sulfide (PbS) CQD and single layer graphene (SG). The inclusion of graphene interlayers is shown to increase power conversion efficiency by 9.18%. It is shown that the inclusion of conductive graphene enhances charge extraction in devices. Photoluminescence shows that graphene quenches emission from the quantum dot suggesting spontaneous charge transfer to graphene. CQD photodetectors exhibit increased photoresponse and improved transport properties. We propose that the CQD/SG hybrid structure is a route to make CQD thin films with improved charge extraction, therefore resulting in improved solar cell efficiency.

Poly(3-hexylthiophene-2,5-diyl) as a Hole Transport Layer for Colloidal Quantum Dot Solar Cells.

Lead sulfide colloidal quantum dot (CQD) solar cells demonstrate extremely high short-circuit currents (Jsc) and are making decent progress in power conversion efficiencies. However, the low fill factors (FF) and open-circuit voltages have to be addressed with urgency to prevent the stalling of efficiency improvements. This paper highlights the importance of improving hole extraction, which received much less attention as compared to the electron-accepting component of the device architecture (e.g., TiO2 or ZnO). Here, we show the use of semiconducting polymer poly(3-hexylthiophene-2,5-diyl) to create efficient CQD devices by improving hole transport, removing interfacial barriers, and minimizing shunt pathways, thus resulting in an overall improvement in device performance stemming from better Jsc and FF.

Transfer printed silver nanowire transparent conductors for PbS-ZnO heterojunction quantum dot solar cells.

Transfer-printed silver nanowire transparent conducting electrodes are demonstrated in lead sulfide-zinc oxide quantum dot solar cells. Advantages of using this transparent conductor technology are increased junction surface energy, solution processing, and the potential cost reduction of low temperature processing. Joule heating, device aging, and film thickness effects are investigated to understand shunt pathways created by nanowires protruding perpendicular to the film. A V(oc) of 0.39 ± 0.07 V, J(sc) of 16.2 ± 0.2 mA/cm(2), and power conversion efficiencies of 2.8 ± 0.4% are presented.