Darren Chi Jin Neo

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.

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.

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.

The emerging technology of colloidal quantum dot electronics provides an opportunity for combining the advantages of well-understood inorganic semiconductors with the chemical processability of molecular systems. So far, most research on quantum dot electronic devices has focused on materials based on Pb- and Cd chalcogenides. In addition to environmental concerns associated with the presence of toxic metals, these quantum dots are not well suited for applications in CMOS circuits due to difficulties in integrating complementary n- and p-channel transistors in a common quantum dot active layer. Here, we demonstrate that by using heavy-metal-free CuInSe₂ quantum dots, we can address the problem of toxicity and simultaneously achieve straightforward integration of complimentary devices to prepare functional CMOS circuits. Specifically, utilizing the same spin-coated layer of CuInSe₂ quantum dots, we realize both p- and n-channel transistors and demonstrate well-behaved integrated logic circuits with low switching voltages compatible with standard CMOS electronics.

The performance of devices containing colloidal quantum dot (CQD) films is strongly dependent on the surface chemistry of the CQDs they contain. Multi-step 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 EDT (1,2-ethanedithiol) ligands. Using lab-based and synchrotron-radiation-excited XPS, we examine the compositions of the surface layer before and after treatment, and correlate this with 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.

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.