Thermal Disorder-Induced Strain and Carrier Localization Activate Reverse Halide Segregation.

The reversal of halide ions is studied under various conditions. However, the underlying mechanism of heat-induced reversal remains unclear. This work finds that dynamic disorder-induced localization of self-trapped polarons and thermal disorder-induced strain (TDIS) can be co-acting drivers of reverse segregation. Localization of polarons results in an order of magnitude decrease in excess carrier density (polaron population), causing a reduced impact of the light-induced strain (LIS - responsible for segregation) on the perovskite framework. Meanwhile, exposing the lattice to TDIS exceeding the LIS can eliminate the photoexcitation-induced strain gradient, as thermal fluctuations of the lattice can mask the LIS strain. Under continuous 0.1 W cm⁻2 illumination (upon segregation), the strain disorder is estimated to be 0.14%, while at 80 °C under dark conditions, the strain is 0.23%. However, in situ heating of the segregated film to 80 °C under continuous illumination (upon reversal) increases the total strain disorder to 0.25%, where TDIS is likely to have a dominant contribution. Therefore, the contribution of entropy to the system's free energy is likely to dominate, respectively. Various temperature-dependent in situ measurements and simulations further support the results. These findings highlight the importance of strain homogenization for designing stable perovskites under real-world operating conditions.

Enhanced Power Conversion Efficiency via Hybrid Ligand Exchange Treatment of p-Type PbS Quantum Dots.

PbS quantum dot solar cells (QDSCs) have emerged as a promising low-cost, solution-processable solar energy harvesting device and demonstrated good air stability and potential for large-scale commercial implementation. PbS QDSCs achieved a record certified efficiency of 12% in 2018 by utilizing an n+-n-p device structure. However, the p-type layer has generally suffered from low carrier mobility due to the organic ligand 1,2-ethanedithiol (EDT) that is used to modify the quantum dot (QD) surface. The low carrier mobility of EDT naturally limits the device thickness as the carrier diffusion length is limited by the low mobility. Herein, we improve the properties of the p-type layer through a two-step hybrid organic ligand treatment. By treating the p-type layer with two types of ligands, 3-mercaptopropionic acid (MPA) and EDT, the PbS QD surface was passivated by a combination of the two ligands, resulting in an overall improvement in open-circuit voltage, fill factor, and current density, leading to an improvement in the cell efficiency from 7.0 to 10.4% for the champion device. This achievement was a result of the improved QD passivation and a reduction in the interdot distance, improving charge transport through the p-type PbS quantum dot film.

Influence of long-range forces and capillarity on the function of underwater superoleophobic wrinkled surfaces.

Underwater superoleophobic surfaces can be considered a particular type of lubricant-infused surface, that have anti-fouling properties by virtue of a trapped water layer that repels oils. However, as their function relies on a water layer being trapped in the surface roughness, it is crucial to understand the factors that determine the layer stability. In this work, the forces that are responsible for the stability of thin liquid films within structured surfaces were quantified, and the conclusions were tested against the performance of wrinkled surfaces as underwater superoleophobic coatings. Here, the system studied was a family of wrinkled surfaces made of hydrophilic poly(4-vinylpyridine) (P4VP), whereby the wrinkle width could be controllably tuned in the range 90 nm to 8000 nm. The van der Waals free energy was quantified and the capillary forces trapping water in the surface micro- and nano-wrinkle structure were estimated. P4VP surfaces with micro-scale wrinkles had underwater superoleophobic properties, and low adhesion to different oils with droplet roll-off angle below 6° ± 1°. Despite the van der Waals free energy of the system pointing to the dewetting of a water film under oil on top of a smooth P4VP film, the wrinkled structure is sufficient to induce a Cassie state with a trapped water layer. The micro-scale wrinkles (average width 4-12 µm) were found to be particularly effective in the trapping of the water in a Cassie non-adhesive state. The P4VP wrinkled surfaces are superamphiphobic, as when they were first infused with oil, and then exposed to a droplet of water under oil, they exhibited superhydrophobic behavior. The P4VP wrinkles have the additional useful feature of being transparent underwater, which makes them useful candidates for the protection of underwater cameras and sensors.

From Lead(II) Dithiocarbamate Precursors to a Fast Response PbS Positive Temperature Coefficient Thermistor.

PbS submicron crystals were formed by thermolysis of two different lead dithiocarbamate complexes. These precursors were readily synthesized and fully characterized, and in situ synchrotron powder diffraction experiments were performed to characterize their decomposition. The structure and purity of resultant PbS was examined using scanning electron and transmission electron microscopies, powder X-ray diffraction, and infrared spectroscopy. Submicron crystalline PbS was used to create a new PbS thermistor with excellent sensitivity and an ultrarapid thermal response time.

Photomechanical photochromism in a cetyltrimethylammonium isopolytungstate.

The photochromic properties of a hybrid compound comprised of the surfactant cation cetyltrimethylammonium [(C16H33)N(CH3)3]+ (CTA+) and the isopolytungstate anion [H2W12O40]6- is investigated. The compound, which has the nominal formula (CTA)7[H2W12O40]Cl·2H2O, changes from white to blue when exposed to UV radiation. The sample returns to the bleached state if stored in the dark-ambient. Application of XPS indicates that the coloring species are WV and WIV. The CTA+ component is found by XPS and FTIR to undergo progressive and irreversible oxidation during this cycle. Examination of FTIR suggests that the changes occur at multiple sites across the amphiphile. Surprisingly, the photochromic cycle is correlated with changes in the X-ray diffraction pattern, indicating partially reversible changes in the ordering of the Keggin ions and their spacing. In particular, application of the UV radiation causes the progressive accumulation of strain in the [001] direction. This is due to permanent oxidative changes in the CTA+ accumulating from cycle to cycle, resulting in an increase in interlamellar-distance due to less interdigitation of the chains. This provides a controllable photomechanical response.

Extending the applicability of the four-flux radiative transfer method.

A generalized four-flux method capable of modeling and tuning the spectral reflectance of a diverse range of complex composite coatings is presented. An example application is exploring and maximizing the visible and near-infrared (IR) spectral reflectance available from the diverse structures arising from combinations of the many practical paint ingredients that are available or can be made when applied to different substrates. This requires consideration of scatterers that can differ in composition, particle size, size distribution, and fill factor, and are held in place by a variety of organic binders, which typically partially absorb in the near IR. This extended model is further enhanced by an explicit matrix algorithm that allows analysis of diverse multilayer stacks. This is applied to a multilayer and is designed to model useful changes that result from varying the pigment fill factor as a function of depth within a layer. What we believe is a novel feature is the way the scattering affects matrix absorptance. The model includes contributions to total absorptance from the scattering pigments and from the paint binder that can arise in different bands or simultaneously at the same wavelengths. Model accuracy is demonstrated by example results when compared to experimental data on dried single layer paint profiles using imaged cross sections. The model input covering the actual pigment and binder properties used are material, shape, size, and size distributions, mass added, and the measured optical constants from 400 nm to 2,500 nm of the undoped binder resin layer. One interesting result is the comparison of a two-layered stack, with bigger particles in the first layer and smaller ones in the second, to one with the opposite depth profile.

Author Correction: Radiative recombination of confined electrons at the MgZnO/ZnO heterojunction interface.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Radiative recombination of confined electrons at the MgZnO/ZnO heterojunction interface.

We investigate the optical signature of the interface in a single MgZnO/ZnO heterojunction, which exhibits two orders of magnitude lower resistivity and 10 times higher electron mobility compared with the MgZnO/Al2O3 film grown under the same conditions. These impressive transport properties are attributed to increased mobility of electrons at the MgZnO/ZnO heterojunction interface. Depth-resolved cathodoluminescence and photoluminescence studies reveal a 3.2 eV H-band optical emission from the heterointerface, which exhibits excitonic properties and a localization energy of 19.6 meV. The emission is attributed to band-bending due to the polarization discontinuity at the interface, which leads to formation of a triangular quantum well and localized excitons by electrostatic coupling.

Optical properties and oxidation of α-phase Ag-Al thin films.

We investigate a series of Ag-Al thin films containing up to 12 at% Al with the purpose of discovering whether these alloys would be a better choice for nanophotonic applications than pure Ag. Variable angle spectroscopic ellipsometry, AFM, x-ray diffraction and density functional theory are applied to explore and characterize the materials. Electromagnetic simulations of optical properties are used to place the results into a theoretical framework. We find that the increase in electron-to-atom ratio associated with the Al additions changes the optical properties: additions of the order of 1-2 at% Al are beneficial as they are associated with favorable changes in the dielectric function, but for greater additions of Al there is a flattening of the absorption edge and an increase in optical loss. In addition, contents of more than about 2 at% Al are associated with the onset of time-dependent intergranular oxidation, which causes a pronounced dip in the reflectance spectrum at about 2.3-2.4 eV (∼500-540 nm).

Remarkable thermal stability of gold nanoparticles functionalised with ruthenium phthalocyanine complexes.

A gold nanoparticle (AuNP) ruthenium phthalocyanine (RuPc) nanocomposite has been synthesised that exhibits high thermal stability. Electrical resistance measurements revealed that the nanocomposite is stable up to ∼320 °C. Examination of the nanocomposite and the RuPc stabiliser complex using thermogravimetric analysis and differential scanning calorimetry show that the remarkable thermal stability is due to the RuPc molecules, which provide an effective barrier to sintering of the AuNPs.

Electroluminescence from localized defects in zinc oxide: toward electrically driven single photon sources at room temperature.

Single photon sources are required for a wide range of applications in quantum information science, quantum cryptography, and quantum communications. However, the majority of room temperature emitters to date are only excited optically, which limits their proper integration into scalable devices. In this work, we overcome this limitation and present room temperature electrically driven light emission from localized defects in zinc oxide (ZnO) nanoparticles and thin films. The devices emit in the red spectral range and show excellent rectifying behavior. The emission is stable over an extensive period of time, providing an important prerequisite for practical devices. Our results open possibilities for building new ZnO-based quantum integrated devices that incorporate solid-state single photon sources for quantum information technologies.

A Subambient Open Roof Surface under the Mid-Summer Sun.

A novel material open to warm air stays below ambient temperature under maximum solar intensities of mid-summer. It is found to be 11 °C cooler than a commercial white cool roof nearby. A combination of specially chosen polymers and a silver thin film yields values near 100% for both solar reflectance, and thermal emittance at infrared wavelengths from 7.9 to 13 µm.

Quantum-confined single photon emission at room temperature from SiC tetrapods.

Controlled engineering of isolated solid state quantum systems is one of the most prominent goals in modern nanotechnology. In this letter we demonstrate a previously unknown quantum system namely silicon carbide tetrapods. The tetrapods have a cubic polytype core (3C) and hexagonal polytype legs (4H)--a geometry that creates spontaneous polarization within a single tetrapod. Modeling of the tetrapod structures predicts that a bound exciton should exist at the 3C-4H interface. The simulations are confirmed by the observation of fully polarized and narrowband single photon emission from the tetrapods at room temperature. The single photon emission provides important insights into understanding the quantum confinement effects in non-spherical nanostructures. Our results pave the way to a new class of crystal phase nanomaterials that exhibit single photon emission at room temperature and therefore are suitable for sensing, quantum information and nanophotonics.

Impacts of Post-metallisation Processes on the Electrical and Photovoltaic Properties of Si Quantum Dot Solar Cells.

As an important step towards the realisation of silicon-based tandem solar cells using silicon quantum dots embedded in a silicon dioxide (SiO(2)) matrix, single-junction silicon quantum dot (Si QD) solar cells on quartz substrates have been fabricated. The total thickness of the solar cell material is 420 nm. The cells contain 4 nm diameter Si quantum dots. The impacts of post-metallisation treatments such as phosphoric acid (H(3)PO(4)) etching, nitrogen (N(2)) gas anneal and forming gas (Ar: H(2)) anneal on the cells' electrical and photovoltaic properties are investigated. The Si QD solar cells studied in this work have achieved an open circuit voltage of 410 mV after various processes. Parameters extracted from dark I-V, light I-V and circular transfer length measurement (CTLM) suggest limiting mechanism in the Si QD solar cell operation and possible approaches for further improvement.