Identifying Luminescent Boron Vacancies in h-BN Generated Using Controlled He+ Ion Irradiation.

The defect emission from h-BN at 1.55 eV is interesting as it enables optical readout of spins. It is necessary to identify the nature of the relevant point defects for its controlled introduction. However, it is challenging to engineer point defects in h-BN without changing the local atomic structure. Here, we controllably introduce boron vacancies in h-BN using an ultrahigh spatial resolution and low-energy He+ ion beam. By optimizing the He+ ion irradiation conditions, we control the quantity and location of defects spatially and along the depth of h-BN to achieve a robust photoluminescence emission at 1.55 eV from 10 K to room temperature. We show that as-generated defects activate an additional Raman mode at 1295 cm-1. Electron energy loss spectroscopy confirms introduction of boron vacancies without modification of the local h-BN crystal structure. Our results provide a deterministic strategy to create scalable boron vacancy emitters in h-BN for quantum photonics.

Tunable Optical Properties of Thin Films Controlled by the Interface Twist Angle.

Control of materials properties has been the driving force of modern technologies. So far, materials properties have been modulated by their composition, structure, and size. Here, by using cathodoluminescence in a scanning transmission electron microscope, we show that the optical properties of stacked, >100 nm thick hexagonal boron nitride (hBN) films can be continuously tuned by their relative twist angles. Due to the formation of a moiré superlattice between the two interface layers of the twisted films, a new moiré sub-band gap is formed with continuously decreasing magnitude as a function of the twist angle, resulting in tunable luminescence wavelength and intensity increase of >40×. Our results demonstrate that moiré phenomena extend beyond monolayer-based systems and can be preserved in a technologically relevant, bulklike material at room temperature, dominating optical properties of hBN films for applications in medicine, environmental, or information technologies.

Nanoscale Modification of WS2 Trion Emission by Its Local Electromagnetic Environment.

Structural, electronic, and chemical nanoscale modifications of transition metal dichalcogenide monolayers alter their optical properties. A key missing element for complete control is a direct spatial correlation of optical response to nanoscale modifications due to the large gap in spatial resolution between optical spectroscopy and nanometer-resolved techniques. Here, we bridge this gap by obtaining nanometer-resolved optical properties using electron spectroscopy at cryogenic temperatures, specifically electron energy loss spectroscopy for absorption and cathodoluminescence for emission, which are then directly correlated to chemical and structural information. In an h-BN/WS2/h-BN heterostructure, we observe local modulation of the trion (X-) emission due to tens of nanometer wide dielectric patches. Trion emission also increases in regions where charge accumulation occurs, close to the carbon film supporting the heterostructures. The localized exciton emission (L) detected here is not correlated to strain above 1%, suggesting point defects might be involved in their formation.

Light Management in Organic Photovoltaics Processed in Ambient Conditions Using ZnO Nanowire and Antireflection Layer with Nanocone Array.

Low carrier mobility and lifetime in semiconductor polymers are some of the main challenges facing the field of organic photovoltaics (OPV) in the quest for efficient devices with high current density. Finding novel strategies such as device structure engineering is a key pathway toward addressing this issue. In this work, the light absorption and carrier collection of OPV devices are improved by employment of ZnO nanowire (NW) arrays with an optimum NW length (50 nm) and antireflection (AR) film with nanocone structure. The optical characterization results show that ZnO NW increases the transmittance of the electron transporting layer as well as the absorption of the polymer blend. Moreover, the as-deposited polymer blend on the ZnO NW array shows better charge transfer as compared to the planar sample. By employing PC70BM:PV2000 as a promising air-stable active-layer, power conversion efficiencies of 9.8% and 10.1% are achieved for NW devices without and with an AR film, indicating 22.5% and 26.2% enhancement in PCE as compared to that of planar device. Moreover, it is shown that the AR film enhances the water-repellent ability of the OPV device.

Minority Carrier Transport in Lead Sulfide Quantum Dot Photovoltaics.

Lead sulfide quantum dots (PbS QDs) are an attractive material system for the development of low-cost photovoltaics (PV) due to their ease of processing and stability in air, with certified power conversion efficiencies exceeding 11%. However, even the best PbS QD PV devices are limited by diffusive transport, as the optical absorption length exceeds the minority carrier diffusion length. Understanding minority carrier transport in these devices will therefore be critical for future efficiency improvement. We utilize cross-sectional electron beam-induced current (EBIC) microscopy and develop methodology to quantify minority carrier diffusion length in PbS QD PV devices. We show that holes are the minority carriers in tetrabutylammonium iodide (TBAI)-treated PbS QD films due to the formation of a p-n junction with an ethanedithiol (EDT)-treated QD layer, whereas a heterojunction with n-type ZnO forms a weaker n+-n junction. This indicates that modifying the standard device architecture to include a p-type window layer would further boost the performance of PbS QD PV devices. Furthermore, quantitative EBIC measurements yield a lower bound of 110 nm for the hole diffusion length in TBAI-treated PbS QD films, which informs design rules for planar and ordered bulk heterojunction PV devices. Finally, the low-energy EBIC approach developed in our work is generally applicable to other emerging thin-film PV absorber materials with nanoscale diffusion lengths.

Room Temperature Sensing Achieved by GaAs Nanowires and oCVD Polymer Coating.

Novel structures comprised of GaAs nanowire arrays conformally coated with conducting polymers (poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3,4-ethylenedioxythiophene-co-3-thiophene acetic acid) display both sensitivity and selectivity to a variety of volatile organic chemicals. A key feature is room temperature operation, so that neither a heater nor the power it would consume, is required. It is a distinct difference from traditional metal oxide sensors, which typically require elevated operational temperature. The GaAs nanowires are prepared directly via self-seeded metal-organic chemical deposition, and conducting polymers are deposited on GaAs nanowires using oxidative chemical vapor deposition (oCVD). The range of thickness for the oCVD layer is between 100 and 200 nm, which is controlled by changing the deposition time. X-ray diffraction analysis indicates an edge-on alignment of the crystalline structure of the PEDOT coating layer on GaAs nanowires. In addition, the positive correlation between the improvement of sensitivity and the increasing nanowire density is demonstrated. Furthermore, the effect of different oCVD coating materials is studied. The sensing mechanism is also discussed with studies considering both nanowire density and polymer types. Overall, the novel structure exhibits good sensitivity and selectivity in gas sensing, and provides a promising platform for future sensor design.

Impacts of Ion Segregation on Local Optical Properties in Mixed Halide Perovskite Films.

Despite the recent astronomical success of organic-inorganic perovskite solar cells (PSCs), the impact of microscale film inhomogeneities on device performance remains poorly understood. In this work, we study CH3NH3PbI3 perovskite films using cathodoluminescence in scanning transmission electron microscopy and show that localized regions with increased cathodoluminescence intensity correspond to iodide-enriched regions. These observations constitute direct evidence that nanoscale stoichiometric variations produce corresponding inhomogeneities in film cathodoluminescence intensity. Moreover, we observe the emergence of high-energy transitions attributed to beam induced iodide segregation, which may mirror the effects of ion migration during PSC operation. Our results demonstrate that such ion segregation can fundamentally change the local optical and microstructural properties of organic-inorganic perovskite films in the course of normal device operation and therefore address the observed complex and unpredictable behavior in PSC devices.

Dimensional Tailoring of Hydrothermally Grown Zinc Oxide Nanowire Arrays.

Hydrothermally synthesized ZnO nanowire arrays are critical components in a range of nanostructured semiconductor devices. The device performance is governed by relevant nanowire morphological parameters that cannot be fully controlled during bulk hydrothermal synthesis due to its transient nature. Here, we maintain homeostatic zinc concentration, pH, and temperature by employing continuous flow synthesis and demonstrate independent tailoring of nanowire array dimensions including areal density, length, and diameter on device-relevant length scales. By applying diffusion/reaction-limited analysis, we separate the effect of local diffusive transport from the c-plane surface reaction rate and identify direct incorporation as the c-plane growth mechanism. Our analysis defines guidelines for precise and independent control of the nanowire length and diameter by operating in rate-limiting regimes. We validate its utility by using surface adsorbents that limit reaction rate to obtain spatially uniform vertical growth rates across a patterned substrate.

Diffusion-Mediated Synthesis of MoS2/WS2 Lateral Heterostructures.

Controlled growth of two-dimensional transition metal dichalcogenide (TMD) lateral heterostructures would enable on-demand tuning of electronic and optoelectronic properties in this new class of materials. Prior to this work, compositional modulations in lateral TMD heterostructures have been considered to depend solely on the growth chronology. We show that in-plane diffusion can play a significant role in the chemical vapor deposition of MoS2/WS2 lateral heterostructures leading to a variety of nontrivial structures whose composition does not necessarily follow the growth order. Optical, structural, and compositional studies of TMD crystals captured at different growth temperatures and in different diffusion stages suggest that compositional mixing versus segregation are favored at high and low growth temperatures, respectively. The observed diffusion mechanism will expand the realm of possible lateral heterostructures, particularly ones that cannot be synthesized using traditional methods.

Mapping of Strain Fields in GaAs/GaAsP Core-Shell Nanowires with Nanometer Resolution.

We report the nanoscale quantification of strain in GaAs/GaAsP core-shell nanowires. By tracking the shifting of higher-order Laue zone (HOLZ) lines in convergent beam electron diffraction patterns, we observe unique variations in HOLZ line separation along different facets of the core-shell structure, demonstrating the nonuniform strain fields created by the heterointerface. Furthermore, through the use of continuum mechanical modeling and Bloch wave analysis we calculate expected HOLZ line shift behavior, which are directly matched to experimental results. This comparison demonstrates both the power of electron microscopy as a platform for nanoscale strain characterization and the reliability of continuum models to accurately calculate complex strain fields in nanoscale systems.

Impact of nucleation conditions on diameter modulation of GaAs nanowires.

Diameter-modulated nanowires can be used to impart unique properties to nanowire-based devices. Here, diameter modulation along Au-seeded GaAs nanowires was achieved by varying the flux of the III and V precursors during growth. Furthermore, three different types of [111]B-oriented nanowires were observed to display distinct differences in diameter modulation, growth rate, and cross-sectional shape. These differences are attributed to the presence of multiple distinct Au-Ga seed particle phases at the growth temperature of 420 °C. We show that the diameter modulation behavior can be modified by the growth conditions during nanowire nucleation, including temperature, V/III ratio, substrate orientation, and seed particle size. These results demonstrate the general viability of flow-controlled diameter modulation for compound semiconductors and highlight both opportunities and challenges that can arise from using compound-forming alloys to seed nanowire growth.

Control of zinc oxide nanowire array properties with electron-beam lithography templating for photovoltaic applications.

Hydrothermally synthesized zinc oxide nanowire arrays have been used as nanostructured acceptors in emerging photovoltaic (PV) devices. The nanoscale dimensions of such arrays allow for enhanced charge extraction from PV active layers, but the device performance critically depends on the nanowire array pitch and alignment. In this study, we templated hydrothermally-grown ZnO nanowire arrays via high-resolution electron-beam-lithography defined masks, achieving the dual requirements of high-resolution patterning at a pitch of several hundred nanometers, while maintaining hole sizes small enough to control nanowire array morphology. We investigated several process conditions, including the effect of annealing sputtered and spincoated ZnO seed layers on nanowire growth, to optimize array property metrics-branching from individual template holes and off-normal alignment. We found that decreasing template hole size decreased branching prevalence but also reduced alignment. Annealing seed layers typically improved alignment, and sputtered seed layers yielded nanowire arrays superior to spincoated seed layers. We show that these effects arose from variation in the size of the template holes relative to the ZnO grain size in the seed layer. The quantitative control of branching and alignment of the nanowire array that is achieved in this study will open new paths toward engineering more efficient electrodes to increase photocurrent in nanostructured PVs. This control is also applicable to inorganic nanowire growth in general, nanomechanical generators, nanowire transistors, and surface-energy engineering.

Flexible graphene electrode-based organic photovoltaics with record-high efficiency.

Advancements in the field of flexible high-efficiency solar cells and other optoelectronic devices will strongly depend on the development of electrode materials with good conductivity and flexibility. To address chemical and mechanical instability of currently used indium tin oxide (ITO), graphene has been suggested as a promising flexible transparent electrode but challenges remain in achieving high efficiency of graphene-based polymer solar cells (PSCs) compared to their ITO-based counterparts. Here we demonstrate graphene anode- and cathode-based flexible PSCs with record-high power conversion efficiencies of 6.1 and 7.1%, respectively. The high efficiencies were achieved via thermal treatment of MoO3 electron blocking layer and direct deposition of ZnO electron transporting layer on graphene. We also demonstrate graphene-based flexible PSCs on polyethylene naphthalate substrates and show the device stability under different bending conditions. Our work paves a way to fully graphene electrode-based flexible solar cells using a simple and reproducible process.

Controlled modulation of diameter and composition along individual III-V nitride nanowires.

Semiconducting nanowires have unique properties that are distinct from their bulk counterparts, but realization of their full potential will be ultimately dictated by the ability to control nanowire structure, composition, and size with high accuracy. Here, we report a simple, yet versatile, approach to modulate in situ the diameter, length, and composition of individual segments within (In,Ga)N nanowires by tuning the seed particle supersaturation and size via the supply of III and V sources during the growth. By elucidating the underlying mechanisms controlling structural evolution, we demonstrate the synthesis of axial InN/InGaN nanowire heterojunctions in the nonpolar m-direction. Our approach can be applied to other materials systems and provides a foundation for future development of complex nanowire structures with enhanced functionality.

Fundamental insights into nanowire diameter modulation and the liquid/solid interface.

Controlled modulation of diameter along the axis of nanowires can enhance nanowire-based device functionality, but the potential for achieving such structures with arbitrary diameter ratios has not been explored. Here, we use a theoretical approach that considers changes in the volume, wetting angle, and three-dimensional morphology of seed particles during nanowire growth to understand and guide nanowire diameter modulation. We use our experimental results from diameter-modulated InN and GaN nanowires and extend our analysis to consider the potential and limitations for diameter modulation in other materials systems. We show that significant diameter modulations can be promoted for seed materials that enable substantial compositional and surface energy changes. Furthermore, we apply our model to provide insights into the morphology of the liquid/solid interface. Our approach can be used to understand and guide nanowire diameter modulation, as well as probe fundamental phenomena during nanowire growth.

Heteroepitaxial growth of GaP/ZnS nanocable with superior optoelectronic response.

We demonstrate the controlled growth of coaxial nanocables composed of GaP/ZnS core-shell structures by a facile chemical vapor deposition method. Structural analysis confirms that the cubic GaP (111) plane and wurtzite ZnS (0001) plane present close similarities in terms of hexagonal-arranged atomic configuration with small in-plane lattice mismatch, and the ZnS shell is epitaxially grown on the (100) plane of the cubic GaP core. Compared with the unitary ZnS nanobelts, the GaP/ZnS coaxial nanocables exhibit improved optoelectronic properties such as high photocurrent and excellent photocurrent stability. This approach opens up new strategy to boost the performance of ZnS-based photodetectors.

Graphene cathode-based ZnO nanowire hybrid solar cells.

Growth of semiconducting nanostructures on graphene would open up opportunities for the development of flexible optoelectronic devices, but challenges remain in preserving the structural and electrical properties of graphene during this process. We demonstrate growth of highly uniform and well-aligned ZnO nanowire arrays on graphene by modifying the graphene surface with conductive polymer interlayers. On the basis of this structure, we then demonstrate graphene cathode-based hybrid solar cells using two different photoactive materials, PbS quantum dots and the conjugated polymer P3HT, with AM 1.5G power conversion efficiencies of 4.2% and 0.5%, respectively, approaching the performance of ITO-based devices with similar architectures. Our method preserves beneficial properties of graphene and demonstrates that it can serve as a viable replacement for ITO in various photovoltaic device configurations.

Structure and exfoliation mechanism of two-dimensional boron nanosheets.

Exfoliation of two-dimensional (2D) nanosheets from three-dimensional (3D) non-layered, non-van der Waals crystals represents an emerging strategy for materials engineering that could significantly increase the library of 2D materials. Yet, the exfoliation mechanism in which nanosheets are derived from crystals that are not intrinsically layered remains unclear. Here, we show that planar defects in the starting 3D boron material promote the exfoliation of 2D boron sheets-by combining liquid-phase exfoliation, aberration-corrected scanning transmission electron microscopy, Raman spectroscopy, and density functional theory calculations. We demonstrate that 2D boron nanosheets consist of a planar arrangement of icosahedral sub-units cleaved along the {001} planes of ß-rhombohedral boron. Correspondingly, intrinsic stacking faults in 3D boron form parallel layers of faulted planes in the same orientation as the exfoliated nanosheets, reducing the {001} cleavage energy. Planar defects represent a potential engineerable pathway for exfoliating 2D sheets from 3D boron and, more broadly, the other covalently bonded materials.

Programmable Interfacial Band Configuration in WS2/Bi2O2Se Heterojunctions.

van der Waals heterojunctions based on transition-metal dichalcogenides (TMDs) offer advanced strategies for manipulating light-emitting and light-harvesting behaviors. A crucial factor determining the light-material interaction is in the band alignment at the heterojunction interface, particularly the distinctions between type-I and type-II alignments. However, altering the band alignment from one type to another without changing the constituent materials is exceptionally difficult. Here, utilizing Bi2O2Se with a thickness-dependent band gap as a bottom layer, we present an innovative strategy for engineering interfacial band configurations in WS2/Bi2O2Se heterojunctions. In particular, we achieve tuning of the band alignment from type-I (Bi2O2Se straddling WS2) to type-II and finally to type-I (WS2 straddling Bi2O2Se) by increasing the thickness of the Bi2O2Se bottom layer from monolayer to multilayer. We verified this band architecture conversion using steady-state and transient spectroscopy as well as density functional theory calculations. Using this material combination, we further design a sophisticated band architecture incorporating both type-I (WS2 straddles Bi2O2Se, fluorescence-quenched) and type-I (Bi2SeO5 straddles WS2, fluorescence-recovered) alignments in one sample through focused laser beam (FLB). By programming the FLB trajectory, we achieve a predesigned localized fluorescence micropattern on WS2 without changing its intrinsic atomic structure. This effective band architecture design strategy represents a significant leap forward in harnessing the potential of TMD heterojunctions for multifunctional photonic applications.

Selenium segregation in femtosecond-laser hyperdoped silicon revealed by electron tomography.

Doping of silicon with chalcogens (S, Se, Te) by femtosecond laser irradiation to concentrations well above the solubility limit leads to near-unity optical absorptance in the visible and infrared (IR) range and is a promising route toward silicon-based IR optoelectronics. However, open questions remain about the nature of the IR absorptance and in particular about the impact of the dopant distribution and possible role of dopant diffusion. Here we use electron tomography using a high-angle annular dark-field (HAADF) detector in a scanning transmission electron microscope (STEM) to extract information about the three-dimensional distribution of selenium dopants in silicon and correlate these findings with the optical properties of selenium-doped silicon. We quantify the tomography results to extract information about the size distribution and density of selenium precipitates. Our results show correlation between nanoscale distribution of dopants and the observed sub-band gap optical absorptance and demonstrate the feasibility of HAADF-STEM tomography for the investigation of dopant distribution in highly-doped semiconductors.