Autonomous atmospheric water seeping MOF matrix.

The atmosphere contains an abundance of fresh water, but this resource has yet to be harvested efficiently. To date, passive atmospheric water sorbents have required a desorption step that relies on steady solar irradiation. Since the availability and intensity of solar radiation vary, these limit on-demand desorption and hence the amount of harvestable water. Here, we report a polymer-metal-organic framework that provides simultaneous and uninterrupted sorption and release of atmospheric water. The adaptable nature of the hydro-active polymer, and its hybridization with a metal-organic framework, enables enhanced sorption kinetics, water uptake, and spontaneous water oozing. We demonstrate continuous water delivery for 1440 hours, producing 6 g of fresh water per gram of sorbent at 90% relative humidity (RH) per day without active condensation. This leads to a total liquid delivery efficiency of 95% and an autonomous liquid delivery efficiency of 71%, the record among reported atmospheric water harvesters.

Effect of disorder on transport properties in a tight-binding model for lead halide perovskites.

The hybrid organic-inorganic lead halide perovskite materials have emerged as remarkable materials for photovoltaic applications. Their strengths include good electric transport properties in spite of the disorder inherent in them. Motivated by this observation, we analyze the effects of disorder on the energy eigenstates of a tight-binding model of these materials. In particular, we analyze the spatial extension of the energy eigenstates, which is quantified by the inverse participation ratio. This parameter exhibits a tendency, and possibly a phase transition, to localization as the on-site energy disorder strength is increased. However, we argue that the disorder in the lead halide perovskites corresponds to a point in the regime of highly delocalized states. Our results also suggest that the electronic states of mixed-halide materials tend to be more localized than those of pure materials, which suggests a weaker tendency to form extended bonding states in the mixed-halide materials and is therefore not favourable for halide mixing.

Power-free, digital and programmable dispensing of picoliter droplets using a Digit Chip.

There is a growing need for power-free methods to manipulate small volumes of liquids and thereby enable use of diagnostic assays in resource-limited settings. Most existing self-powered devices provide analog manipulation of fluids using paper, capillary or pressure-driven pumps. These strategies are well-suited to manipulating larger micro- and milliliter-scale volumes at constant flow rates; however, they fail to enable the manipulation of nanoliter and picoliter volumes required in assays using droplets, capillary sampling (e.g. finger prick), or expensive reagents. Here we report a device, termed the Digit Chip, that provides programmable and power-free digital manipulation of sub-nanoliter volumes. The device consists of a user-friendly button interface and a series of chambers connected by capillary valves that serve as digitization elements. Via a button press, the user dispenses and actuates ultra-small, quantitatively-programmed volumes. The device geometry is optimized using design models and experiments and precisely dispenses volumes as low as 21 pL with 97% accuracy. The volume dispensed can be tuned in 10 discrete steps across one order-of-magnitude with 98% accuracy. As a proof-of-principle that nanoliter-scale reagents can be precisely actuated and combined on-chip, we deploy the device to construct a precise concentration gradient with 10 discrete concentrations. Additionally, we apply this device alongside an inexpensive smartphone-based fluorescence imaging platform to perform a titration of E. coli with ampicillin. We observe the onset of bacterial death at a concentration of 5 µg mL-1, increasing to a maximum at 50 µg mL-1. These results establish the utility of the Digit Chip for diagnostic applications in low-resource environments.

Broadband Epsilon-near-Zero Reflectors Enhance the Quantum Efficiency of Thin Solar Cells at Visible and Infrared Wavelengths.

The engineering of broadband absorbers to harvest white light in thin-film semiconductors is a major challenge in developing renewable materials for energy harvesting. Many solution-processed materials with high manufacturability and low cost, such as semiconductor quantum dots, require the use of film structures with thicknesses on the order of 1 µm to absorb incoming photons completely. The electron transport lengths in these media, however, are 1 order of magnitude smaller than this length, hampering further progress with this platform. Herein, we show that, by engineering suitably disordered nanoplasmonic structures, we have created a new class of dispersionless epsilon-near-zero composite materials that efficiently harness white light. Our nanostructures localize light in the dielectric region outside the epsilon-near-zero material with characteristic lengths of 10-100 nm, resulting in an efficient system for harvesting broadband light when a thin absorptive film is deposited on top of the structure. By using a combination of theory and experiments, we demonstrate that ultrathin layers down to 50 nm of colloidal quantum dots deposited atop the epsilon-near-zero material show an increase in broadband absorption ranging from 200% to 500% compared to a planar structure of the same colloidal quantum-dot-absorber average thickness. When the epsilon-near-zero nanostructures were used in an energy-harvesting module, we observed a spectrally averaged 170% broadband increase in the external quantum efficiency of the device, measured at wavelengths between 400 and 1200 nm. Atomic force microscopy and photoluminescence excitation measurements demonstrate that the properties of these epsilon-near-zero structures apply to general metals and could be used to enhance the near-field absorption of semiconductor structures more widely. We have developed an inexpensive electrochemical deposition process that enables scaled-up production of this nanomaterial for large-scale energy-harvesting applications.

Atomistic model of fluorescence intermittency of colloidal quantum dots.

Optoelectronic applications of colloidal quantum dots demand a high emission efficiency, stability in time, and narrow spectral bandwidth. Electronic trap states interfere with the above properties but understanding of their origin remains lacking, inhibiting the development of robust passivation techniques. Here we show that surface vacancies improve the fluorescence yield compared to vacancy-free surfaces, while dynamic vacancy aggregation can temporarily turn fluorescence off. We find that infilling with foreign cations can stabilize the vacancies, inhibiting intermittency and improving quantum yield, providing an explanation of recent experimental observations.

Dynamic Trap Formation and Elimination in Colloidal Quantum Dots.

Using first-principles simulations on PbS and CdSe colloidal quantum dots, we find that surface defects form in response to electronic doping and charging of the nanoparticles. We show that electronic trap states in nanocrystals are dynamic entities, in contrast with the conventional picture wherein traps are viewed as stable electronic states that can be filled or emptied, but not created or destroyed. These traps arise from the formation or breaking of atomic dimers at the nanoparticle surface. The dimers' energy levels can reside within the bandgap, in which case a trap is formed. Fortunately, we are also able to identify a number of shallow-electron-affinity cations that stabilize the surface, working to counter dynamic trap formation and allowing for trap-free doping.

A solution-processed 1.53 mum quantum dot laser with temperature-invariant emission wavelength.

Sources of coherent, monochromatic short-wavelength infrared (1-2 mum) light are essential in telecommunications, biomedical diagnosis, and optical sensing. Today's semiconductor lasers are made by epitaxial growth on a lattice-matched single-crystal substrate. This strategy is incompatible with integration on silicon. Colloidal quantum dots grown in solution can, in contrast, be coated onto any surface. Here we show a 1.53 mum laser fabricated using a remarkably simple process: dipping a glass capillary into a colloidal suspension of semiconductor quantum dots. We developed the procedures to produce a smooth, low-scattering-loss film inside the capillary, resulting in a whispering gallery mode laser with a well-defined threshold. While there exist three prior reports of optical gain in infrared-emitting colloidal quantum dots [1,2,3], this work represents the first report of an infrared laser made using solution processing. We also report dlambda(max)/dT, the temperature-sensitivity of lasing wavelength, of 0.03 nm/K, the lowest ever reported in a colloidal quantum dot system and 10 times lower than in traditional semiconductor quantum wells.

Room-temperature amplified spontaneous emission at 1300 nm in solution-processed PbS quantum-dot films.

We report room-temperature amplified spontaneous emission and spectral narrowing at infrared wavelengths in solution-processed films made up of PbS quantum-dot nanocrystals. The results are relevant to optical amplification and lasing integrated upon a variety of substrates. The active optical medium operates at room temperature without any additional matrix material, providing an optical gain of 260 cm(-1) and a pump threshold of 1 mJ/cm(-2). Nanocrystals synthesized in an aqueous solution and stabilized by use of short ligands result in high quantum-dot volume fractions in solid films and in a redshift emission relative to absorption.

Optical control over photoconductivity in polyferrocenylsilane films.

We report the study and elucidate the origin of the photoconductivity of polyferrocenylsilanes achieved through photooxidation performed by ultraviolet irradiation in the presence of chloroform. The persistence over months of the changes in the optoelectronic properties allowed more detailed studies of the charge photogeneration process. The photocurrent spectrum mimics that of the absorption indicating that the photooxidized material is not a mechanical mixture of oxidized and unoxidized polymer units. Photomodulation spectroscopy revealed the existence of long-lived photoexcited states with a lifetime in the millisecond range. They have been interpreted as trapped excitons at the oxidized sites where the polymer is deformed due to the presence of the chloroform derived counter ions. Because of the relatively long lifetime of the trapped excitons they can dissociate and the formed charge carriers can be separated in an externally applied electric field. The effect of the polymer chain deformation around the oxidized unit extends over the neighboring polymer units. In light of the potential applications of this class of polymers in various electronic and photonic devices, the clarification of such a basic process as the photocurrent generation will be a key factor for further technological development.

Time-resolved luminescence in conducting polymer/antidot nanocomposites.

We report modification of the structure and properties of conjugated polymers through controlled embedding wide-gap nanocrystals (antidots) within the polymer matrix. Investigations were carried out by means of stationary and time-resolved photoluminescence. Antidots strongly modify the luminescence spectrum of poly(p-phenylene vinylene) but have almost no influence on the spectrum of poly(2-(6-cyano-6'-methylheptyloxy)-1, 4-phenylene. We explain this observation with respect to the different chain structure and electron density distribution in these two materials. The temporal evolution of luminescence spectra in polymer/antidot composites contains a series of characteristic times. The shortest of these (0.35-0.6 ns) are independent of antidot material and characterize processes in the polymer matrix. Larger times considerably exceeding 1 ns are composition-sensitive and attributable to carrier capture by nanocrystals. The qualitative character of the modification of luminescence spectra associated with the inclusion of antidots depends strongly on the characteristics of the polymer matrices and more weakly on the antidot material. This suggests that the predominant effect of the nanocrystals relates to the modification of the matrix near the polymer-inorganic interface.