Evaluating Modified Ultrasound-Guided Serratus Anterior Plane Block for Enhanced Postoperative Recovery in Thoracoscopic Lobectomy Patients.

BACKGROUND Thoracoscopic lobectomy is accompanied by intense trauma and pain due to impaired chest wall integrity. We aimed to introduce a modified ultrasound-guided serratus anterior plane block (MUG-SAPB) for postoperative analgesia in patients who underwent thoracoscopic lobectomy, and to determine whether it could effectively alleviate postoperative pain and improve recovery quality. MATERIAL AND METHODS Overall, 78 patients randomly received either combined MUG-SAPB (0.25% ropivacaine, 10 mg dexamethasone, 40 mL) with patient-controlled intravenous analgesia (PCIA) or received PCIA alone. The primary outcomes were visual analog scale (VAS) scores at rest and during movement at 4, 8, 12, 20, 24, 48, and 72 h postoperatively. The secondary outcomes included use of opioids during surgery, numbers of rescue analgesics (butorphanol), frequency of patient-controlled analgesia (PCA), comfort score within 24 h postoperatively, and postoperative complications within 72 h. RESULTS Compared to the PCIA group, in the MUG-SAPB group, resting VAS scores at 4-24 h (P<0.05) and movement VAS scores at 4-12 h postoperatively (P<0.05) were lower; intraoperative use of sufentanil and frequency of PCA were less, and less rescue analgesia was used (P=0.02, P=0.04 and P=0.03, respectively). Patients in the MUG-SAPB group had faster first mobilization (P=0.04). The MUG-SAPB group had higher comfort scores than the PCIA group (P=0.03). None of the MUG-SAPB patients had any SAPB-related complications. CONCLUSIONS MUG-SAPB effectively relieved postoperative pain, reduced opioid consumption, and accelerated early ambulation in comparison with PCIA alone in patients who underwent thoracoscopic lobectomy.

Synthesis of Honeycomb-Structured Beryllium Oxide via Graphene Liquid Cells.

Using high-resolution transmission electron microscopy and electron energy-loss spectroscopy, we show that beryllium oxide crystallizes in the planar hexagonal structure in a graphene liquid cell by a wet-chemistry approach. These liquid cells can feature van-der-Waals pressures up to 1 GPa, producing a miniaturized high-pressure container for the crystallization in solution. The thickness of as-received crystals is beyond the thermodynamic ultra-thin limit above which the wurtzite phase is energetically more favorable according to the theoretical prediction. The crystallization of the planar phase is ascribed to the near-free-standing condition afforded by the graphene surface. Our calculations show that the energy barrier of the phase transition is responsible for the observed thickness beyond the previously predicted limit. These findings open a new door for exploring aqueous-solution approaches of more metal-oxide semiconductors with exotic phase structures and properties in graphene-encapsulated confined cells.

Engineering Edge States of Graphene Nanoribbons for Narrow-Band Photoluminescence.

Solid-state narrow-band light emitters are on-demand for quantum optoelectronics. Current approaches based on defect engineering in low-dimensional materials usually introduce a broad range of emission centers. Here, we report narrow-band light emission from covalent heterostructures fused to the edges of graphene nanoribbons (GNRs) by controllable on-surface reactions from molecular precursors. Two types of heterojunction (HJ) states are realized by sequentially synthesizing GNRs and graphene nanodots (GNDs) and then coupling them together. HJs between armchair GNDs and armchair edges of the GNR are coherent and give rise to narrow-band photoluminescence. In contrast, HJs between the armchair GNDs and the zigzag ends of GNRs are defective and give rise to nonradiative states near the Fermi level. At low temperatures, sharp photoluminescence emissions with peak energy range from 2.03 to 2.08 eV and line widths of 2-5 meV are observed. The radiative HJ states are uniform, and the optical transition energy is controlled by the band gaps of GNRs and GNDs. As these HJs can be synthesized in a large quantity with atomic precision, this finding highlights a route to programmable and deterministic creation of quantum light emitters.

Peculiar bond characters of fivefold coordinated octet compound crystals.

The present work exemplifies complementary perspectives offered by the band and bond pictures of solids, with an emphasis on the chemical intuition pertaining to the latter, especially in the presence of interfaces. The modern computational method of constructing a unique set of maximally localized Wannier functions from delocalized band states imparts new interpretations to the familiar concept of chemical bonds in the context of crystalline solids. By bridging the band and bond pictures using advanced computational tools, we reveal for the first time the unusual bond characters of a long-predicted fivefold coordinated structure of binary octet compounds A N B8-N consisting of AA' stacked planar AB honeycombs. While the isolated monolayer retains the familiar p z -π bonding in a honeycomb framework as in graphene and hexagonal boron nitride, the bulk foregoes in-plane π bonding and embraces out-of-plane ⋯A-B-A-B⋯ chain bonding via overlapping p z orbitals. Not only does the chemical intuition gained by invoking the bond picture clarify the chemical nature of the fivefold coordination, but it also facilely explains a salient discrepancy in theoretical predictions in otherwise sound ample experimental evidence in the form of epitaxial thin films, paving the way towards rational synthesis of such thin films for optoelectronic applications. On the other hand, we show that the conduction band minimum, important in determining the electrical and optical properties, is a distinctly extended state that can only be properly described within the band picture.

Multifunctional metaoptics based on bilayer metasurfaces.

Optical metasurfaces have become versatile platforms for manipulating the phase, amplitude, and polarization of light. A platform for achieving independent control over each of these properties, however, remains elusive due to the limited engineering space available when using a single-layer metasurface. For instance, multiwavelength metasurfaces suffer from performance limitations due to space filling constraints, while control over phase and amplitude can be achieved, but only for a single polarization. Here, we explore bilayer dielectric metasurfaces to expand the design space for metaoptics. The ability to independently control the geometry and function of each layer enables the development of multifunctional metaoptics in which two or more optical properties are independently designed. As a proof of concept, we demonstrate multiwavelength holograms, multiwavelength waveplates, and polarization-insensitive 3D holograms based on phase and amplitude masks. The proposed architecture opens a new avenue for designing complex flat optics with a wide variety of functionalities.

Direct imaging of the nitrogen-rich edge in monolayer hexagonal boron nitride and its band structure tuning.

Identification of edge atoms and tracking the edge structure evolution of two-dimensional (2D) crystals at the scale of individual atoms is critical for understanding the edge-dominated properties and behavioral responses to external field stimuli. Here, direct imaging of the edge configuration of monolayer hexagonal boron nitride (h-BN) is demonstrated at the atomic scale, by using aberration-corrected transmission electron microscopy. Tracking of the edge atoms revealed that a nitrogen-terminated zigzag arrangement dominates along the edge, naturally leading to nitrogen rich (N-rich) characteristics in this area, while the stoichiometric interior of the h-BN monolayer is maintained. Both top-down fabrication and bottom-up growth were proposed to obtain novel h-BN flakes with an N-rich ratio larger than 1% when the size is reduced to the threshold of 25 nm. Furthermore, density functional theory calculations revealed that a new bandgap of ∼3 eV is created by the N-rich characteristics, and h-BN transforms into an n-type semiconductor by self-doping. The results call for the development of ultra-small h-BN islands to be used in intriguing 2D electronic devices with a photoresponse function to visible light.

Multilayer Noninteracting Dielectric Metasurfaces for Multiwavelength Metaoptics.

Metasurfaces provide a versatile platform for manipulating the wavefront of light using planar nanostructured surfaces. Transmissive metasurfaces, with full 2π phase control, are a particularly attractive platform for replacing conventional optical elements due to their small footprint and broad functionality. However, the operational bandwidth of metasurfaces has been a critical limitation and is directly connected to either their resonant response or the diffractive dispersion of their lattice. While multiwavelength and continuous band operation have been demonstrated, the elements suffer from either low efficiency, reduced imaging quality, or limited element size. Here, we propose a platform that provides for multiwavelength operation by employing tightly spaced multilayer dielectric metasurfaces. As a proof of concept, we demonstrate a multiwavelength metalens doublet (NA = 0.42) with focusing efficiencies of 38% and 52% at wavelengths of 1180 and 1680 nm, respectively. We further show how this approach can be extended to three-wavelength metalenses as well as a spectral splitter. This approach could find applications in fluorescent microscopy, digital imaging, and color routing.

Green's function for a sharpened and metal-coated dielectric probe.

In apertureless scanning-probe optical microscopy and in the case of more traditional scanned optical probes coated with a metal that is thin near the probe tip (in lieu of an aperture), samples are probed via interaction between the probe and surface. In the nanometer-scale region between the tip and the sample, the field can be approximated by quasi-electrostatic analytics. Hence, the coated probe can be modeled as in the present case as a hyperboloid of revolution without the need for hyperboloidal wave functions in the near zone. The solutions to Laplace's equation and in general Green's function with the application of the boundary conditions, therefore, yield an appropriate approximation and allow a completely analytical solution for the resonance effects upon the probe tip to be obtained. The large field enhancements due to the sharpness of the tip and to surface plasmon fields may thus be analytically examined.

Unraveling the Fundamental Mechanisms of Solvent-Additive-Induced Optimization of Power Conversion Efficiencies in Organic Photovoltaic Devices.

The realization of controllable morphologies of bulk heterojunctions (BHJ) in organic photovoltaics (OPVs) is one of the key factors enabling high-efficiency devices. We provide new insights into the fundamental mechanisms essential for the optimization of power conversion efficiencies (PCEs) with additive processing to PBDTTT-CF:PC71BM system. We have studied the underlying mechanisms by monitoring the 3D nanostructural modifications in BHJs and correlated the modifications with the optical analysis and theoretical modeling of charge transport. Our results demonstrate profound effects of diiodooctane (DIO) on morphology and charge transport in the active layers. For small amounts of DIO (<3 vol %), DIO promotes the formation of a well-mixed donor-acceptor compact film and augments charge transfer and PCE. In contrast, for large amounts of DIO (>3 vol %), DIO facilitates a loosely packed mixed morphology with large clusters of PC71BM, leading to deterioration in PCE. Theoretical modeling of charge transport reveals that DIO increases the mobility of electrons and holes (the charge carriers) by affecting the energetic disorder and electric field dependence of the mobility. Our findings show the implications of phase separation and carrier transport pathways to achieve optimal device performances.

Tunneling spectra of graphene on copper unraveled.

Scanning tunneling spectroscopy is often employed to study two-dimensional (2D) materials on conductive growth substrates, in order to gain information on the electronic structures of the 2D material-substrate systems, which can lead to insight into 2D material-substrate interactions, growth mechanisms, etc. The interpretation of the spectra can be complicated, however. Specifically for graphene grown on copper, there have been conflicting reports of tunneling spectra. A clear understanding of the mechanisms behind the variability is desired. In this work, we have revealed that the root cause of the variability in tunneling spectra is the variation in graphene-substrate coupling under various experimental conditions, providing a salutary perspective on the important role of 2D material-substrate interactions. The conclusions are drawn from measured data and theoretical calculations for monolayer, AB-stacked bilayer, and twisted bilayer graphene coexisting on the same substrates in areas with and without intercalated oxygen, demonstrating a high degree of consistency. The Van Hove singularities of the twisted graphene unambiguously indicate the Dirac energy between them, lending strong evidence to our assignment of the spectral features. In addition, we have discovered an O-Cu superstructure that has never been observed before.

Peculiarity of Two Thermodynamically-Stable Morphologies and Their Impact on the Efficiency of Small Molecule Bulk Heterojunction Solar Cells.

Structural characteristics of the active layers in organic photovoltaic (OPV) devices play a critical role in charge generation, separation and transport. Here we report on morphology and structural control of p-DTS(FBTTh2)2:PC71BM films by means of thermal annealing and 1,8-diiodooctane (DIO) solvent additive processing, and correlate it to the device performance. By combining surface imaging with nanoscale depth-sensitive neutron reflectometry (NR) and X-ray diffraction, three-dimensional morphologies of the films are reconstituted with information extending length scales from nanometers to microns. DIO promotes the formation of a well-mixed donor-acceptor vertical phase morphology with a large population of small p-DTS(FBTTh2)2 nanocrystals arranged in an elongated domain network of the film, thereby enhancing the device performance. In contrast, films without DIO exhibit three-sublayer vertical phase morphology with phase separation in agglomerated domains. Our findings are supported by thermodynamic description based on the Flory-Huggins theory with quantitative evaluation of pairwise interaction parameters that explain the morphological changes resulting from thermal and solvent treatments. Our study reveals that vertical phase morphology of small-molecule based OPVs is significantly different from polymer-based systems. The significant enhancement of morphology and information obtained from theoretical modeling may aid in developing an optimized morphology to enhance device performance for OPVs.

Correlating high power conversion efficiency of PTB7:PC71BM inverted organic solar cells with nanoscale structures.

Advances in material design and device engineering led to inverted organic solar cells (i-OSCs) with superior power conversion efficiencies (PCEs) compared to their "conventional" counterparts, in addition to the well-known better ambient stability. Here, we report an in-depth morphology study of the i-OSC active and cathode modifying layers, employing a model system with a well-established bulk-heterojunction, PTB7:PC71BM as the active layer and poly-[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) as the cathode surface modifying layer. We have also identified the role of a processing additive, 1,8-diiodooctane (DIO), used in the spin-casting of the active layer to increase PCE. Using various characterization techniques, we demonstrate that the high PCEs of i-OSCs are due to the diffusion of electron-accepting PC71BM into the PFN layer, resulting in improved electron transport. The diffusion occurs when residual solvent molecules in the spun-cast film act as a plasticizer. Addition of DIO to the casting solution results in more PC71BM diffusion and therefore more efficient electron transport. This work provides important insight and guidance to further enhancement of i-OSC performance by materials and interface engineering.

Spatially resolved one-dimensional boundary states in graphene-hexagonal boron nitride planar heterostructures.

Two-dimensional interfaces between crystalline materials have been shown to generate unusual interfacial electronic states in complex oxides. Recently, a one-dimensional interface has been realized in hexagonal boron nitride and graphene planar heterostructures, where a polar-on-nonpolar one-dimensional boundary is expected to possess peculiar electronic states associated with edge states of graphene and the polarity of boron nitride. Here we present a combined scanning tunnelling microscopy and first-principles theory study of the graphene-boron nitride boundary to provide a first glimpse into the spatial and energetic distributions of the one-dimensional boundary states down to atomic resolution. The revealed boundary states are about 0.6 eV below or above the Fermi level depending on the termination of the boron nitride at the boundary, and are extended along but localized at the boundary. These results suggest that unconventional physical effects similar to those observed at two-dimensional interfaces can also exist in lower dimensions.

Unusual role of epilayer-substrate interactions in determining orientational relations in van der Waals epitaxy.

Using selected-area low-energy electron diffraction analysis, we showed strict orientational alignment of monolayer hexagonal boron nitride (h-BN) crystallites with Cu(100) surface lattices of Cu foil substrates during atmospheric pressure chemical vapor deposition. In sharp contrast, the graphene-Cu(100) system is well-known to assume a wide range of rotations despite graphene's crystallographic similarity to h-BN. Our density functional theory calculations uncovered the origin of this surprising difference: The crystallite orientation is determined during nucleation by interactions between the cluster's edges and the substrate. Unlike the weaker B- and N-Cu interactions, strong C-Cu interactions rearrange surface Cu atoms, resulting in the aligned geometry not being a distinct minimum in total energy. The discovery made in this specific case runs counter to the conventional wisdom that strong epilayer-substrate interactions enhance orientational alignment in epitaxy and sheds light on the factors that determine orientational relation in van der Waals epitaxy of 2D materials.

Heteroepitaxial growth of two-dimensional hexagonal boron nitride templated by graphene edges.

By adapting the concept of epitaxy to two-dimensional space, we show the growth of a single-atomic-layer, in-plane heterostructure of a prototypical material system--graphene and hexagonal boron nitride (h-BN). Monolayer crystalline h-BN grew from fresh edges of monolayer graphene with atomic lattice coherence, forming an abrupt one-dimensional interface, or boundary. More important, the h-BN lattice orientation is solely determined by the graphene, forgoing configurations favored by the supporting copper substrate.

Synthesis of millimeter-size hexagon-shaped graphene single crystals on resolidified copper.

We present a facile method to grow millimeter-size, hexagon-shaped, monolayer, single-crystal graphene domains on commercial metal foils. After a brief in situ treatment, namely, melting and subsequent resolidification of copper at atmospheric pressure, a smooth surface is obtained, resulting in the low nucleation density necessary for the growth of large-size single-crystal graphene domains. Comparison with other pretreatment methods reveals the importance of copper surface morphology and the critical role of the melting-resolidification pretreatment. The effect of important growth process parameters is also studied to determine their roles in achieving low nucleation density. Insight into the growth mechanism has thus been gained. Raman spectroscopy and selected area electron diffraction confirm that the synthesized millimeter-size graphene domains are high-quality monolayer single crystals with zigzag edge terminations.

Surface-induced orientation control of CuPc molecules for the epitaxial growth of highly ordered organic crystals on graphene.

The epitaxial growth and preferred molecular orientation of copper phthalocyanine (CuPc) molecules on graphene has been systematically investigated and compared with growth on Si substrates, demonstrating the role of surface-mediated interactions in determining molecular orientation. X-ray scattering and diffraction, scanning tunneling microscopy, scanning electron microscopy, and first-principles theoretical calculations were used to show that the nucleation, orientation, and packing of CuPc molecules on films of graphene are fundamentally different compared to those grown on Si substrates. Interfacial dipole interactions induced by charge transfer between CuPc molecules and graphene are shown to epitaxially align the CuPc molecules in a face-on orientation in a series of ordered superstructures. At high temperatures, CuPc molecules lie flat with respect to the graphene substrate to form strip-like CuPc crystals with micrometer sizes containing monocrystalline grains. Such large epitaxial crystals may potentially enable improvement in the device performance of organic thin films, wherein charge transport, exciton diffusion, and dissociation are currently limited by grain size effects and molecular orientation.