The reported photocurrent density (JSC) of PbS quantum dot (QD)-sensitized solar cell was less than 19 mA/cm2 despite the capability to generate 38 mA/cm2, which results from inefficient electron injection and fast charge recombination. Here, we report on a PbS:Hg QD-sensitized solar cell with an unprecedentedly high JSC of 30 mA/cm2. By Hg2+ doping into PbS, JSC is almost doubled with improved stability. Femtosecond transient study confirms that the improved JSC is due to enhanced electron injection and suppressed charge recombination. EXAFS reveals that Pb-S bond is reinforced and structural disorder is reduced by interstitially incorporated Hg2+, which is responsible for the enhanced electron injection, suppressed recombination and stability. Thanks to the extremely high JSC, power conversion efficiency of 5.6% is demonstrated at one sun illumination.

Layered assembly structures composed of nanomaterials, such as nanocrystals, have attracted considerable attention as promising candidates for new functional devices whose optical, electromagnetic and electronic behaviours are determined by the spatial arrangement of component elements. However, difficulties in handling each constituent layer in a materialspecific manner limit the 3D integration of disparate nanomaterials into the appropriate heterogeneous electronics. Here we report a pick-and-place transfer method that enables the transfer of large-area nanodot assemblies. This solvent-free transfer utilizes a lifting layer and allows for the reliable transfer of a quantum dot (QD) monolayer, enabling layer-by-layer design. With the controlled multistacking of different bandgap QD layers, we are able to probe the interlayer energy transfer among different QD monolayers. By controlling the emission spectrum through such designed monolayer stacking, we have achieved white emission with stable optoelectronic properties, the closest to pure white among the QD lightemitting diodes reported so far.

Femtosecond two-dimensional infrared (2D IR) spectroscopy has been applied to study the conformations of a model dipeptide, N-acetyl-L-prolinamide (AcProNH2) in deuterated chloroform (CDCl3). Spectral features in the amide-I and -II regions are obtained by rephasing (R), nonrephasing (NR), and reverse photon echo (RPE) pulse sequences with two polarization conditions. The 2D spectra obtained by the RPE and NR sequences with (0, 0, 0, 0) polarization reveal new spectral features associated with the multiple conformers of AcProNH2 that are difficult to discern using R sequence and linear-IR spectroscopy. The high resolving power of the RPE sequence comes from destructive interference between the positive and negative peaks of nearby vibrators, similar to the NR sequence. The RPE response functions that are useful for 2D spectral simulations are evaluated, including the effects of vibrational frequency correlations. The 2D spectra obtained with (45, -45, 90, 0) polarization exhibit clear cross-peak patterns in the off-diagonal region for the R and RPE sequences but in the diagonal region for the NR sequence. These patterns, free from strong diagonal contributions, are crucial for structure determination. DFT calculations, normal-mode analysis, Hessian matrix reconstruction, and vibrational exciton Hamiltonian diagonalization yield molecular parameters needed for quantitative simulations of 2D spectra: angles between transition dipoles, coupling constants, and off-diagonal anharmonicities of the amide-I and -II modes are obtained for solvated trans-C7 and cis structures and for gas-phase trans conformers in the region of phi = -120 degrees to 0 degrees and psi = -100 degrees to 180 degrees in the Ramachandran space. Systematic simulations based on a 4:1 population ratio of the solvated trans-C7 and cis structures reproduce well the 2D spectral features obtained at both polarization conditions. However, better agreement between the experimental and simulated cross-peak patterns can be reached if the dihedral angles of the major trans conformer are close to (phi, psi) = (-80 degrees , 100 degrees ). Our results suggest that the major conformer of AcProNH2 in CDCl3 deviates from the gas-phase global minimum, the trans-C7 form, to an extended intermediate between the C7 and polyproline-II structure. These results are discussed in relationship with earlier findings obtained by NMR, transient IR studies, and MD simulations.

Degradation of organic materials is responsible for the short operation lifetimes of organic light-emitting devices, but the mechanism by which such degradation is initiated has yet to be fully established. Here we report a new mechanism for degradation of emitting layers in blue-phosphorescent devices. We investigate binary mixtures of a wide bandgap host and a series of novel Ir(III) complex dopants having N-heterocyclocarbenic ligands. Our mechanistic study reveals the charge-neutral generation of polaron pairs (radical ion pairs) by electron transfer from the dopant to host excitons. Annihilation of the radical ion pair occurs by charge recombination, with such annihilation competing with bond scission. Device lifetime correlates linearly with the rate constant for the annihilation of the radical ion pair. Our findings demonstrate the importance of controlling exciton-induced electron transfer, and provide novel strategies to design materials for long-lifetime blue electrophosphorescence devices.

The structural, electrical, and optical properties of monolayer ruthenium oxide (RuO 2 ) nanosheets (NSs) fabricated by chemical exfoliation of a layered three-dimensional form of K-intercalated RuO 2 are studied systematically via experimental and computational methods. Monolayer RuO 2 NS is identified as having a distorted h-MX 2 structure. This is the first observation of a RuO 2 NS structure that is unlike the t-MX 2 structure of the RuO 2 layers in the parent material and does not have hexagonal symmetry. The distorted h-MX 2 RuO 2 NSs are shown to have optical transparency superior to that of graphene, thereby predicting the feasibility of applying RuO 2 NSs to flexible transparent electrodes. In addition, it is demonstrated that the semiconducting band structures of RuO 2 NSs can be manipulated to be semimetallic by adjusting the crystal structure, which is related to band-gap engineering. This finding indicates that RuO 2 NSs can be used in a variety of applications, such as flexible transparent electrodes, atomic-layer devices, and optoelectronic devices.