Free Charge Carrier Generation by Visible-Light-Absorbing Organic Spacers in Ruddlesden-Popper Layered Perovskites.

Incorporating organic semiconductor building blocks as spacer cations into layered hybrid perovskites provides an opportunity to develop new materials with novel optoelectronic properties, including nanoheterojunctions that afford spatial separation of electron and hole transport. However, identifying organics with suitable structure and electronic energy levels to selectively absorb visible light has been a challenge in the field. In this work, we introduce a new lead-halide-based Ruddlesden-Popper perovskite structure based on a visible-light-absorbing naphthalene-iminoimide cation (NDI-DAE). Thin films of (NDI-DAE)2PbI4 show a quenched photoluminescence and transient absorption dynamics consistent with the formation of a charge transfer state or free charge carriers when either the inorganic or organic layer is photoexcited, suggesting the formation of a type II nanoheterostructure. Time-resolved microwave conductivity analysis supports free charge generation with sum mobilities up to 4 × 10-4 cm2 V-1 s-1. Mixed halide (NDI-DAE)2Pb(IxBr1-x)4 films show modified inorganic layer band gaps and a photoluminescent reversed type I nanoheterostructure with high bromide content (e.g., for x = 0). At x = 0.5, transient absorption and microwave conductivity measurements provide strong evidence that selective visible-light absorbance by the NDI-DAE cation generates separated free carriers via hole transfer to the inorganic layer (leaving photogenerated electrons in the organic layer), which represents an important step toward enhancing light harvesting and affording the spatial separation of charge carrier transport in stable layered perovskite-based devices.

Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

Extraction of mobile charge carrier photogeneration yield spectrum of ultrathin-film metal oxide photoanodes for solar water splitting.

Light absorption in strongly correlated electron materials can excite electrons and holes into a variety of different states. Some of these excitations yield mobile charge carriers, whereas others result in localized states that cannot contribute to photocurrent. The photogeneration yield spectrum, ξ(λ), represents the wavelength-dependent ratio between the contributing absorption that ultimately generates mobile charge carriers and the overall absorption. Despite being a vital material property, it is not trivial to characterize. Here, we present an empirical method to extract ξ(λ) through optical and external quantum efficiency measurements of ultrathin films. We applied this method to haematite photoanodes for water photo-oxidation, and observed that it is self-consistent for different illumination conditions and applied potentials. We found agreement between the extracted ξ(λ) spectrum and the photoconductivity spectrum measured by time-resolved microwave conductivity. These measurements revealed that mobile charge carrier generation increases with increasing energy across haematite's absorption spectrum. Low-energy non-contributing absorption fundamentally limits the photoconversion efficiency of haematite photoanodes and provides an upper limit to the achievable photocurrent that is substantially lower than that predicted based solely on absorption above the bandgap. We extended our analysis to TiO2 and BiVO4 photoanodes, demonstrating the broader utility of the method for determining ξ(λ).

A high-throughput chromatin immunoprecipitation approach reveals principles of dynamic gene regulation in mammals.

Understanding the principles governing mammalian gene regulation has been hampered by the difficulty in measuring in vivo binding dynamics of large numbers of transcription factors (TF) to DNA. Here, we develop a high-throughput Chromatin ImmunoPrecipitation (HT-ChIP) method to systematically map protein-DNA interactions. HT-ChIP was applied to define the dynamics of DNA binding by 25 TFs and 4 chromatin marks at 4 time-points following pathogen stimulus of dendritic cells. Analyzing over 180,000 TF-DNA interactions we find that TFs vary substantially in their temporal binding landscapes. This data suggests a model for transcription regulation whereby TF networks are hierarchically organized into cell differentiation factors, factors that bind targets prior to stimulus to prime them for induction, and factors that regulate specific gene programs. Overlaying HT-ChIP data on gene-expression dynamics shows that many TF-DNA interactions are established prior to the stimuli, predominantly at immediate-early genes, and identified specific TF ensembles that coordinately regulate gene-induction.

Charge carrier dynamics and photocatalytic activity of {111} and {100} faceted Ag3PO4 particles.

Silver orthophosphate is a highly promising visible light photocatalyst with high quantum yield for solar driven water oxidation. Recently, the performance of this material has been further enhanced using facet-controlled synthesis. The tetrahedral particles with {111} exposed facets demonstrate higher photocatalytic performance than the cubic particles with {100} exposed facets. However, the reason behind this large difference in photocatalytic performance is still not understood. In this work, we study the free charge carrier dynamics, such as mobility, lifetime, and diffusion lengths, for the {111}-faceted tetrahedral and the {100}-faceted cubic particles using time-resolved microwave conductivity measurements. An order of magnitude higher charge carrier mobility and diffusion length are found for the tetrahedral particles as compared to the cubic particles. The differences in crystal structure, surface composition, and optical properties are investigated in order to understand how these properties impact the charge carrier dynamics and the photocatalytic performance of differently faceted particles.

Gradient Self-Doped CuBi2O4 with Highly Improved Charge Separation Efficiency.

A new strategy of using forward gradient self-doping to improve the charge separation efficiency in metal oxide photoelectrodes is proposed. Gradient self-doped CuBi2O4 photocathodes are prepared with forward and reverse gradients in copper vacancies using a two-step, diffusion-assisted spray pyrolysis process. Decreasing the Cu/Bi ratio of the CuBi2O4 photocathodes introduces Cu vacancies that increase the carrier (hole) concentration and lowers the Fermi level, as evidenced by a shift in the flat band toward more positive potentials. Thus, a gradient in Cu vacancies leads to an internal electric field within CuBi2O4, which can facilitate charge separation. Compared to homogeneous CuBi2O4 photocathodes, CuBi2O4 photocathodes with a forward gradient show highly improved charge separation efficiency and enhanced photoelectrochemical performance for reduction reactions, while CuBi2O4 photocathodes with a reverse gradient show significantly reduced charge separation efficiency and photoelectrochemical performance. The CuBi2O4 photocathodes with a forward gradient produce record AM 1.5 photocurrent densities for CuBi2O4 up to -2.5 mA/cm2 at 0.6 V vs RHE with H2O2 as an electron scavenger, and they show a charge separation efficiency of 34% for 550 nm light. The gradient self-doping accomplishes this without the introduction of external dopants, and therefore the tetragonal crystal structure and carrier mobility of CuBi2O4 are maintained. Lastly, forward gradient self-doped CuBi2O4 photocathodes are protected with a CdS/TiO2 heterojunction and coated with Pt as an electrocatalyst. These photocathodes demonstrate photocurrent densities on the order of -1.0 mA/cm2 at 0.0 V vs RHE and evolve hydrogen with a faradaic efficiency of ∼91%.

Discovery and characterization of artifactual mutations in deep coverage targeted capture sequencing data due to oxidative DNA damage during sample preparation.

As researchers begin probing deep coverage sequencing data for increasingly rare mutations and subclonal events, the fidelity of next generation sequencing (NGS) laboratory methods will become increasingly critical. Although error rates for sequencing and polymerase chain reaction (PCR) are well documented, the effects that DNA extraction and other library preparation steps could have on downstream sequence integrity have not been thoroughly evaluated. Here, we describe the discovery of novel C > A/G > T transversion artifacts found at low allelic fractions in targeted capture data. Characteristics such as sequencer read orientation and presence in both tumor and normal samples strongly indicated a non-biological mechanism. We identified the source as oxidation of DNA during acoustic shearing in samples containing reactive contaminants from the extraction process. We show generation of 8-oxoguanine (8-oxoG) lesions during DNA shearing, present analysis tools to detect oxidation in sequencing data and suggest methods to reduce DNA oxidation through the introduction of antioxidants. Further, informatics methods are presented to confidently filter these artifacts from sequencing data sets. Though only seen in a low percentage of reads in affected samples, such artifacts could have profoundly deleterious effects on the ability to confidently call rare mutations, and eliminating other possible sources of artifacts should become a priority for the research community.

Resolving electron and hole transport properties in semiconductor materials by constant light-induced magneto transport.

The knowledge of minority and majority charge carrier properties enables controlling the performance of solar cells, transistors, detectors, sensors, and LEDs. Here, we developed the constant light induced magneto transport method which resolves electron and hole mobility, lifetime, diffusion coefficient and length, and quasi-Fermi level splitting. We demonstrate the implication of the constant light induced magneto transport for silicon and metal halide perovskite films. We resolve the transport properties of electrons and holes predicting the material's effectiveness for solar cell application without making the full device. The accessibility of fourteen material parameters paves the way for in-depth exploration of causal mechanisms limiting the efficiency and functionality of material structures. To demonstrate broad applicability, we further characterized twelve materials with drift mobilities spanning from 10-3 to 103 cm2V-1s-1 and lifetimes varying between 10-9 and 10-3 seconds. The universality of our method its potential to advance optoelectronic devices in various technological fields.

Photogenerated charge transfer in Dion-Jacobson type layered perovskite based on naphthalene diimide.

Incorporating organic semiconducting spacer cations into layered lead halide perovskite structures provides a powerful approach to mitigate the typical strong dielectric and quantum confinement effects by inducing charge-transfer between the organic and inorganic layers. Herein we report the synthesis and characterization of thin films of novel DJ-phase organic-inorganic layered perovskite semiconductors using a naphthalene diimide (NDI) based divalent spacer cation, which is shown to accept photogenerated electrons from the inorganic layer. With alkyl chain lengths of 6 carbons, an NDI-based thin film exhibited electron mobility (based on space charge-limited current for quasi-layered 〈n〉 = 5 material) was found to be as high as 0.03 cm2 V-1 s-1 with no observable trap-filling region suggesting trap passivation by the NDI spacer cation.

Activating a Semiconductor-Liquid Junction via Laser-Derived Dual Interfacial Layers for Boosted Photoelectrochemical Water Splitting.

The semiconductor-liquid junction (SCLJ), the dominant place in photoelectrochemical (PEC) catalysis, determines the interfacial activity and stability of photoelectrodes, whcih directly affects the viability of PEC hydrogen generation. Though efforts dedicated in past decades, a challenge remains regarding creating a synchronously active and stable SCLJ, owing to the technical hurdles of simultaneously overlaying the two advantages. The present work demonstrates that creating an SCLJ with a unique configuration of the dual interfacial layers can yield BiVO4 photoanodes with synchronously boosted photoelectrochemical activity and operational stability, with values located at the top in the records of such photoelectrodes. The bespoke dual interfacial layers, accessed via grafting laser-generated carbon dots with phenolic hydroxyl groups (LGCDs-PHGs), are experimentally verified effective, not only in generating the uniform layer of LGCDs with covalent anchoring for inhibited photocorrosion, but also in activating, respectively, the charge separation and transfer in each layer for boosted charge-carrier kinetics, resulting in FeNiOOH-LGCDs-PHGs-MBVO photoanodes with a dual configuration with the photocurrent density of 6.08 mA cm-2 @ 1.23 VRHE , and operational stability up to 120 h @ 1.23 VRHE . Further work exploring LGCDs-PHGs from catecholic molecules warrants the proposed strategy as being a universal alternative for addressing the interfacial charge-carrier kinetics and operational stability of semiconductor photoelectrodes.

CVD grown GaSbxN1-x films as visible-light active photoanodes.

The III-V semiconductor GaN is a promising material for photoelectrochemical (PEC) cells, however the large bandgap of 3.45 eV is a considerable hindrance for the absorption of visible light. Therefore, the substitution of small amounts of N anions by isovalent Sb is a promising route to lower the bandgap and thus increase the PEC activity under visible light. Herein we report a new chemical vapor deposition (CVD) process utilizing the precursors bis(N,N'-diisopropyl-2-methyl-amidinato)-methyl gallium (III) and triphenyl antimony (TPSb) for the growth of GaSbxN1-x alloys. X-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements show crystalline and homogeneous thin films at deposition temperatures in the range of 500-800 °C. Rutherford backscattering spectrometry (RBS) combined with nuclear reaction analysis (NRA) shows an incorporation of 0.2-0.7 at% antimony into the alloy, which results in a slight bandgap decrease (up to 0.2 eV) accompanied by enhanced sub-bandgap optical response. While the resulting photoanodes are active under visible light, the external quantum efficiencies remained low. Intriguingly, the best performing films exhibits the lowest charge carrier mobility according to time resolved THz spectroscopy (TRTS) and microwave conductivity (TRMC) measurements, which showed mobilities of up to 1.75 cm2 V-1 s-1 and 1.2 × 10-2 cm2 V-1 s-1, for each timescale, respectively.

Femtosecond time-resolved two-photon photoemission studies of ultrafast carrier relaxation in Cu2O photoelectrodes.

Cuprous oxide (Cu2O) is a promising material for solar-driven water splitting to produce hydrogen. However, the relatively small accessible photovoltage limits the development of efficient Cu2O based photocathodes. Here, femtosecond time-resolved two-photon photoemission spectroscopy has been used to probe the electronic structure and dynamics of photoexcited charge carriers at the Cu2O surface as well as the interface between Cu2O and a platinum (Pt) adlayer. By referencing ultrafast energy-resolved surface sensitive spectroscopy to bulk data we identify the full bulk to surface transport dynamics for excited electrons rapidly localized within an intrinsic deep continuous defect band ranging from the whole crystal volume to the surface. No evidence of bulk electrons reaching the surface at the conduction band level is found resulting into a substantial loss of their energy through ultrafast trapping. Our results uncover main factors limiting the energy conversion processes in Cu2O and provide guidance for future material development.

Embedding laser generated nanocrystals in BiVO4 photoanode for efficient photoelectrochemical water splitting.

Addressing the intrinsic charge transport limitation of metal oxides has been of significance for pursuing viable PEC water splitting photoelectrodes. Growing a photoelectrode with conductive nanoobjects embedded in the matrix is promising for enhanced charge transport but remains a challenge technically. We herein show a strategy of embedding laser generated nanocrystals in BiVO4 photoanode matrix, which achieves photocurrent densities of up to 5.15 mA cm-2 at 1.23 VRHE (from original 4.01 mA cm-2) for a single photoanode configuration, and 6.22 mA cm-2 at 1.23 VRHE for a dual configuration. The enhanced performance by such embedding is found universal owing to the typical features of laser synthesis and processing of colloids (LSPC) for producing ligand free nanocrystals in desired solvents. This study provides an alternative to address the slow bulk charge transport that bothers most metal oxides, and thus is significant for boosting their PEC water splitting performance.

Author Correction: Highly (001)-textured p-type WSe2 Thin Films as Efficient Large-Area Photocathodes for Solar Hydrogen Evolution.

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

Charge Carrier Lifetimes in Cr-Fe-Al-O Thin Films.

The effect of compositional variation on charge carrier lifetimes of Cr1Fe0.84Al0.16O3, a promising material for solar water splitting recently identified using combinatorial materials science, is explored using ultrafast time-resolved optical reflectance. The transient signal can be described by a biexponential decay, where the shorter time constant varies over 1 order of magnitude with changing Cr content while the longer one stays constant. Intrinsic performance limitations such as a low charge carrier mobility on the order of 10-3 cm2/(Vs) are identified. Charge carrier lifetime and mobility are discussed as screening criteria for solar water splitting materials.

Highly (001)-textured p-type WSe2 Thin Films as Efficient Large-Area Photocathodes for Solar Hydrogen Evolution.

Highly (001)-textured, photoactive WSe2 thin films have been prepared by an amorphous solid-liquid-crystalline solid process promoted by palladium. By increasing the thickness of the Pd promoter film (≥10 nm) the structure and texture of the WSe2 films can be improved significantly. However, these as-crystallized WSe2 films are only weakly photoactive in a 0.5 М H2SO4 electrolyte under AM 1.5 solar irradiation which we attribute to an inefficient photogenerated charge transfer across the WSe2/electrolyte interface via the prevailing van der Waals planes of the WSe2 crystallites. In this work photochemically deposited platinum on the p-type WSe2 photocathode is used for an efficient electron transfer thus inducing the hydrogen evolution reaction. Upon illuminating the WSe2 photocathodes in a Pt-ion containing electrolyte, the photogenerated electrons reduce Pt+ to Pt leading to the precipitation of Pt islands, preferentially at edge steps of the WSe2, i.e. at the grain boundaries of the WSe2 crystallites. The increasing amount of Pt islands at the grain boundaries linearly enhances the photocurrent density up to 2.5 mA cm-2 at 0 VRHE in sulfuric acid, the highest reported value up to now for WSe2 thin films.

Fabrication of Single Crystal Gallium Phosphide Thin Films on Glass.

Due to its high refractive index and low absorption coefficient, gallium phosphide is an ideal material for photonic structures targeted at the visible wavelengths. However, these properties are only realized with high quality epitaxial growth, which limits substrate choice and thus possible photonic applications. In this work, we report the fabrication of single crystal gallium phosphide thin films on transparent glass substrates via transfer bonding. GaP thin films on Si (001) and (112) grown by MOCVD are bonded to glass, and then the growth substrate is removed with a XeF2 vapor etch. The resulting GaP films have surface roughnesses below 1 nm RMS and exhibit room temperature band edge photoluminescence. Magnesium doping yielded p-type films with a carrier density of 1.6 × 1017 cm-3 that exhibited mobilities as high as 16 cm2V-1s-1. Due to their unique optical properties, these films hold much promise for use in advanced optical devices.

MAP kinase pathway alterations in BRAF-mutant melanoma patients with acquired resistance to combined RAF/MEK inhibition.

Treatment of BRAF-mutant melanoma with combined dabrafenib and trametinib, which target RAF and the downstream MAP-ERK kinase (MEK)1 and MEK2 kinases, respectively, improves progression-free survival and response rates compared with dabrafenib monotherapy. Mechanisms of clinical resistance to combined RAF/MEK inhibition are unknown. We performed whole-exome sequencing (WES) and whole-transcriptome sequencing (RNA-seq) on pretreatment and drug-resistant tumors from five patients with acquired resistance to dabrafenib/trametinib. In three of these patients, we identified additional mitogen-activated protein kinase (MAPK) pathway alterations in the resistant tumor that were not detected in the pretreatment tumor, including a novel activating mutation in MEK2 (MEK2(Q60P)). MEK2(Q60P) conferred resistance to combined RAF/MEK inhibition in vitro, but remained sensitive to inhibition of the downstream kinase extracellular signal-regulated kinase (ERK). The continued MAPK signaling-based resistance identified in these patients suggests that alternative dosing of current agents, more potent RAF/MEK inhibitors, and/or inhibition of the downstream kinase ERK may be needed for durable control of BRAF-mutant melanoma.

Whole-exome sequencing and clinical interpretation of formalin-fixed, paraffin-embedded tumor samples to guide precision cancer medicine.

Translating whole-exome sequencing (WES) for prospective clinical use may have an impact on the care of patients with cancer; however, multiple innovations are necessary for clinical implementation. These include rapid and robust WES of DNA derived from formalin-fixed, paraffin-embedded tumor tissue, analytical output similar to data from frozen samples and clinical interpretation of WES data for prospective use. Here, we describe a prospective clinical WES platform for archival formalin-fixed, paraffin-embedded tumor samples. The platform employs computational methods for effective clinical analysis and interpretation of WES data. When applied retrospectively to 511 exomes, the interpretative framework revealed a 'long tail' of somatic alterations in clinically important genes. Prospective application of this approach identified clinically relevant alterations in 15 out of 16 patients. In one patient, previously undetected findings guided clinical trial enrollment, leading to an objective clinical response. Overall, this methodology may inform the widespread implementation of precision cancer medicine.