Memory in quantum dot blinking.

The photoluminescence intermittency (blinking) of quantum dots is interesting because it is an easily measured quantum process whose transition statistics cannot be explained by Fermi's golden rule. Commonly, the transition statistics are power-law distributed, implying that quantum dots possess at least trivial memories. By investigating the temporal correlations in the blinking data, we demonstrate with high statistical confidence that there is nontrivial memory between the on and off brightness duration data of blinking quantum dots. We define nontrivial memory to be statistical complexity greater than one. We show that this memory cannot be discovered using the transition distribution. We show by simulation that this memory does not arise from standard data manipulations. Finally, we conclude that at least three physical mechanisms can explain the measured nontrivial memory: (1) storage of state information in the chemical structure of a quantum dot; (2) the existence of more than two intensity levels in a quantum dot; and (3) the overlap in the intensity distributions of the quantum dot states, which arises from fundamental photon statistics.

Quasiperiodic light.

Quasiperiodicity is a form of spatial order that has been observed in quasicrystalline matter but not light. We construct a quasicrystalline surface out of a light emitting diode. Using a nanoscale waveguide as a microscope (NSOM), we directly image the light field at the surface of the diode. Here we show, using reciprocal space representations of the images, that the light field is quasiperiodic. We explain the structure of the light field with wave superposition. Periodic ordering is limited to at most six-fold symmetry. The light field exhibits 12-fold quasisymmetry, showing order while disproving periodicity. This demonstrates that a new class, consisting of projections from hyperspace, exists in the taxonomy of light ordering.

Optimal quantum dot size for photovoltaics with fusion.

Light fusion increases the efficiency of solar cells by converting photons with lower energy than the bandgap into higher energy photons. The solar cell converts the product photons to current. We use Monte Carlo simulation to predict that lead sulfide (PbS) quantum dot sensitizers will enable fusion with a figure of merit on the mA cm-2 scale, exceeding current records, while enabling silicon cell compatibility. Performance is highly sensitive to quantum dot size, on the order of mA cm-2 nm-1.

Facile purification of CsPbX3 (X = Cl-, Br-, I-) perovskite nanocrystals.

CsPbI3 perovskite nanocrystals are a promising optoelectronic material when stabilized in their cubic phase. While ongoing efforts have addressed this structural challenge through a variety of meta-stabilization approaches, the postsynthesis purification of these nanocrystal dispersions has remained a challenge. In this article, we undertake a detailed investigation into the chemical, optical, and structural changes that arise during purification of CsPbI3 nanocrystals. It is found that nanocrystal degradation can only be avoided through the judicious control of additives within each purification cycle. Under optimized additive-to-nanocrystal ratios, multiple purification cycles can be readily achieved, while retaining the quality and phase stability of the CsPbI3. This facile purification protocol ensures the preparation of high purity and high quality CsPbI3 nanocrystal inks that are suitable for better characterization or integration in optoelectronic devices. The approach has been generalized for CsPbX3 (X = Cl-, Br-, and I-).

Atomistic determination of the surface structure of Cu2O(111): experiment and theory.

Cuprous oxide (Cu2O) is a promising catalyst for several important reactions. However, the atomic structures of defective Cu2O surfaces, which critically affect the catalytic properties both thermodynamically and kinetically, are not unambiguously characterized. High-resolution scanning tunneling microscopy (STM), combined with density functional theory (DFT) calculations and STM simulations, has been used to determine the atomic structure of the (111) surface of a Cu2O bulk crystal. The single crystal surface, processed by ultrahigh vacuum cleaning and oxygen annealing, shows a (1 × 1) periodicity in the low-energy electron diffraction pattern. The pristine (defect-free) Cu2O(111) surface exhibits a lattice of protrusions with hexagonal symmetry under STM, which is attributed to the dangling bonds of the coordinatively unsaturated copper (CuU) atoms on the surface. Two types of surface atomic defects are also identified, including the CuU vacancy and the oxygen-vacancy-induced local surface restructuring. The electronic structure of this surface measured by dI/dV spectroscopy shows an energy band gap of ∼1.6-2.1 eV. Consistent with dI/dV measurements, DFT calculations identified surface states within the electronic band gap arising from the Cu ions on the surface. Our results provide a clear picture of the pristine and defective Cu2O(111) surface structure in addition to the formation mechanism of the reconstructed surface, paving the way toward studying the site-dependent reactivity of this surface.

Photochemical upconversion is suppressed by high concentrations of molecular sensitizers.

Photochemical upconversion uses sensitized triplet-triplet annihilation in bimolecular compositions to convert lower energy photons to higher energy photons. For high efficiency under low illumination, usually a high sensitizer concentration is desirable. However, here we show that the upconversion sensitizer can reduce the emitter triplet lifetime by dynamic quenching, with rate constants on the order 106 M-1 s-1, leading to diminishing returns beyond a certain concentration. These results serve as a warning to designers of photochemical upconvertors that higher concentrations of sensitizers are not necessarily beneficial to upconversion performance.

Endothermic singlet fission is hindered by excimer formation.

Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for a maximum energy-conversion efficiency, and such systems have been considered to form an excimer-like state with multiexcitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, the excimer serves to trap excited states to the detriment of singlet-fission yield. We clearly demonstrate that singlet fission and its conjugate process, triplet-triplet annihilation, occur at a longer intermolecular distance than an excimer intermediate would impute. These results establish that an endothermic singlet-fission material must be designed to avoid excimer formation, thus allowing singlet fission to reach its full potential in enhancing photovoltaic energy conversion.

Ferroelectric Polarization and Second Harmonic Generation in Supramolecular Cocrystals with Two Axes of Charge-Transfer.

Ferroelectricity in organic materials remains a subject of great interest, given its potential impact as lightweight information storage media. Here we report supramolecular charge-transfer cocrystals formed by electron acceptor and donor molecules that exhibit ferroelectric behavior along two distinct crystallographic axes. The solid-state superstructure of the cocrystals reveals that a 2:1 ratio of acceptor to donor molecules assemble into nearly orthogonal mixed stacks in which the molecules are positioned for charge-transfer in face-to-face and edge-to-face orientations, held together by an extended hydrogen-bonding network. Polarization hysteresis was observed along the face-to-face and edge-to-face axes at room temperature. The noncentrosymmetric nature of the cocrystals, required to observe ferroelectric behavior, is demonstrated using second harmonic generation measurements. This finding suggests the possibility of designing supramolecular arrays in which organic molecules support multidimensional information storage.

Structure Evolution and Thermoelectric Properties of Carbonized Polydopamine Thin Films.

Carbonization of nature-inspired polydopamine can yield thin films with high electrical conductivity. Understanding of the structure of carbonized PDA (cPDA) is therefore highly desired. In this study, neutron diffraction, Raman spectroscopy, and other techniques indicate that cPDA samples are mainly amorphous with some short-range ordering and graphite-like structure that emerges with increasing heat treatment temperature. The electrical conductivity and the Seebeck coefficient show different trends with heat treatment temperature, while the thermal conductivity remains insensitive. The largest room-temperature ZT of 2 × 10-4 was obtained on samples heat-treated at 800 °C, which is higher than that of reduced graphene oxide.

Seeing the invisible plasma with transient phonons in cuprous oxide.

The emission of phonons from electron-hole plasma is the primary limit on the efficiency of photovoltaic devices operating above the bandgap. In cuprous oxide (Cu2O) there is no luminescence from electron-hole plasma. Therefore, we searched for optical phonons emitted by energetic charge carriers using phonon-to-exciton upconversion transitions. We found 14 meV phonons with a lifetime of 0.916 ± 0.008 ps and 79 meV phonons that are longer lived and overrepresented. It is surprising that the higher energy phonon has a longer lifetime.

Nickel Confined in the Interlayer Region of Birnessite: an Active Electrocatalyst for Water Oxidation.

We report a synthetic method to enhance the electrocatalytic activity of birnessite for the oxygen evolution reaction (OER) by intercalating Ni(2+) ions into the interlayer region. Electrocatalytic studies showed that nickel (7.7 atomic %)-intercalated birnessite exhibits an overpotential (η) of 400 mV for OER at an anodic current of 10 mA cm(-2) . This η is significantly lower than the η values for birnessite (η≈700 mV) and the active OER catalyst ß-Ni(OH)2 (η≈550 mV). Molecular dynamics simulations suggest that a competition among the interactions between the nickel cation, water, and birnessite promote redox chemistry in the spatially confined interlayer region.

Copper-Intercalated Birnessite as a Water Oxidation Catalyst.

We report a synthetic method to increase the catalytic activity of birnessite toward water oxidation by intercalating copper in the interlayer region of the layered manganese oxide. Intercalation of copper, verified by XRD, XPS, ICP, and Raman spectroscopy, was accomplished by exposing a suspension of birnessite to a Cu(+)-bearing precursor molecule that underwent disproportionation in solution to yield Cu(0) and Cu(2+). Electrocatalytic studies showed that the Cu-modified birnessite exhibited an overpotential for water oxidation of ∼490 mV (at 10 mA/cm(2)) and a Tafel slope of 126 mV/decade compared to ∼700 mV (at 10 mA/cm(2)) and 240 mV/decade, respectively, for birnessite without copper. Impedance spectroscopy results suggested that the charge transfer resistivity of the Cu-modified sample was significantly lower than Cu-free birnessite, suggesting that Cu in the interlayer increased the conductivity of birnessite leading to an enhancement of water oxidation kinetics. Density functional theory calculations show that the intercalation of Cu(0) into a layered MnO2 model structure led to a change of the electronic properties of the material from a semiconductor to a metallic-like structure. This conclusion from computation is in general agreement with the aforementioned impedance spectroscopy results. X-ray photoelectron spectroscopy (XPS) showed that Cu(0) coexisted with Cu(2+) in the prepared Cu-modified birnessite. Control experiments using birnessite that was decorated with only Cu(2+) showed a reduction in water oxidation kinetics, further emphasizing the importance of Cu(0) for the increased activity of birnessite. The introduction of Cu(0) into the birnessite structure also increased the stability of the electrocatalyst. At a working current of 2 mA, the Cu-modified birnessite took ∼3 times longer for the overpotential for water oxdiation to increase by 100 mV compared to when Cu was not present in the birnessite.

Hybrid germanium iodide perovskite semiconductors: active lone pairs, structural distortions, direct and indirect energy gaps, and strong nonlinear optical properties.

The synthesis and properties of the hybrid organic/inorganic germanium perovskite compounds, AGeI3, are reported (A = Cs, organic cation). The systematic study of this reaction system led to the isolation of 6 new hybrid semiconductors. Using CsGeI3 (1) as the prototype compound, we have prepared methylammonium, CH3NH3GeI3 (2), formamidinium, HC(NH2)2GeI3 (3), acetamidinium, CH3C(NH2)2GeI3 (4), guanidinium, C(NH2)3GeI3 (5), trimethylammonium, (CH3)3NHGeI3 (6), and isopropylammonium, (CH3)2C(H)NH3GeI3 (7) analogues. The crystal structures of the compounds are classified based on their dimensionality with 1­4 forming 3D perovskite frameworks and 5­7 1D infinite chains. Compounds 1­7, with the exception of compounds 5 (centrosymmetric) and 7 (nonpolar acentric), crystallize in polar space groups. The 3D compounds have direct band gaps of 1.6 eV (1), 1.9 eV (2), 2.2 eV (3), and 2.5 eV (4), while the 1D compounds have indirect band gaps of 2.7 eV (5), 2.5 eV (6), and 2.8 eV (7). Herein, we report on the second harmonic generation (SHG) properties of the compounds, which display remarkably strong, type I phase-matchable SHG response with high laser-induced damage thresholds (up to ∼3 GW/cm(2)). The second-order nonlinear susceptibility, χS(2), was determined to be 125.3 ± 10.5 pm/V (1), (161.0 ± 14.5) pm/V (2), 143.0 ± 13.5 pm/V (3), and 57.2 ± 5.5 pm/V (4). First-principles density functional theory electronic structure calculations indicate that the large SHG response is attributed to the high density of states in the valence band due to sp-hybridization of the Ge and I orbitals, a consequence of the lone pair activation.

Cupric oxide inclusions in cuprous oxide crystals grown by the floating zone method.

Phase-pure cuprous oxide (Cu2O) crystals are difficult to grow since cupric oxide can form within the crystal as the crystal is cooled to ambient conditions. Vacancies are the solute which causes precipitation of macroscopic defects. Therefore, even when a mostly phase-pure single crystal is used as a feed rod, cupric oxide inclusions persist in the recrystallized solid. Control of the thermal profile during crystal growth, however, can improve phase-purity; a slow counter-rotation rate of the feed and seed rods results in fewer inclusions. Cupric oxide can be removed by annealing, which produces a factor of 540 ± 70 increase in phase-purity.

Third-harmonic generation in cuprous oxide: efficiency determination.

The efficiency of third-harmonic generation in cuprous oxide was measured. Intensities followed a noncubic power law that indicates nonperturbative behavior. Polarization anisotropy of the harmonic generation was demonstrated and related to the third-order susceptibility. The results will influence the understanding of harmonic generation in centrosymmetric materials and are potentially relevant to device design and the interpretation of exciton behavior.