Interfacial epitaxy of multilayer rhombohedral transition-metal dichalcogenide single crystals.

Rhombohedral-stacked transition-metal dichalcogenides (3R-TMDs), which are distinct from their hexagonal counterparts, exhibit higher carrier mobility, sliding ferroelectricity, and coherently enhanced nonlinear optical responses. However, surface epitaxial growth of large multilayer 3R-TMD single crystals is difficult. We report an interfacial epitaxy methodology for their growth of several compositions, including molybdenum disulfide (MoS2), molybdenum diselenide, tungsten disulfide, tungsten diselenide, niobium disulfide, niobium diselenide, and molybdenum sulfoselenide. Feeding of metals and chalcogens continuously to the interface between a single-crystal Ni substrate and grown layers ensured consistent 3R stacking sequence and controlled thickness from a few to 15,000 layers. Comprehensive characterizations confirmed the large-scale uniformity, high crystallinity, and phase purity of these films. The as-grown 3R-MoS2 exhibited room-temperature mobilities up to 155 and 190 square centimeters per volt second for bi- and trilayers, respectively. Optical difference frequency generation with thick 3R-MoS2 showed markedly enhanced nonlinear response under a quasi-phase matching condition (five orders of magnitude greater than monolayers).

Strong chiroptical nonlinearity in coherently stacked boron nitride nanotubes.

Nanomaterials with a large chiroptical response and high structural stability are desirable for advanced miniaturized optical and optoelectronic applications. One-dimensional (1D) nanotubes are robust crystals with inherent and continuously tunable chiral geometries. However, their chiroptical response is typically weak and hard to control, due to the diverse structures of the coaxial tubes. Here we demonstrate that as-grown multiwalled boron nitride nanotubes (BNNTs), featuring coherent-stacking structures including near monochirality, homo-handedness and unipolarity among the component tubes, exhibit a scalable nonlinear chiroptical response. This intrinsic architecture produces a strong nonlinear optical response in individual multiwalled BNNTs, enabling second-harmonic generation (SHG) with a conversion efficiency up to 0.01% and output power at the microwatt level-both excellent figures of merit in the 1D nanomaterials family. We further show that the rich chirality of the nanotubes introduces a controllable nonlinear geometric phase, producing a chirality-dependent SHG circular dichroism with values of -0.7 to +0.7. We envision that our 1D chiral platform will enable novel functions in compact nonlinear light sources and modulators.

Stacking-Controlled Growth of rBN Crystalline Films with High Nonlinear Optical Conversion Efficiency up to 1.

Nonlinear optical crystals lie at the core of ultrafast laser science and quantum communication technology. The emergence of 2D materials provides a revolutionary potential for nonlinear optical crystals due to their exceptionally high nonlinear coefficients. However, uncontrolled stacking orders generally induce the destructive nonlinear response due to the optical phase deviation in different 2D layers. Therefore, conversion efficiency of 2D nonlinear crystals is typically limited to less than 0.01% (far below the practical criterion of >1%). Here, crystalline films of rhombohedral boron nitride (rBN) with parallel stacked layers are controllably synthesized. This success is realized by the utilization of vicinal FeNi (111) single crystal, where both the unidirectional arrangement of BN grains into a single-crystal monolayer and the continuous precipitation of (B,N) source for thick layers are guaranteed. The preserved in-plane inversion asymmetry in rBN films keeps the in-phase second-harmonic generation field in every layer and leads to a record-high conversion efficiency of 1% in the whole family of 2D materials within the coherence thickness of only 1.6 µm. The work provides a route for designing ultrathin nonlinear optical crystals from 2D materials, and will promote the on-demand fabrication of integrated photonic and compact quantum optical devices.

Greatly Enhanced Raman Scattering of Graphene on Metals by a Boron Nitride Film Covering.

Raman spectroscopy, a nondestructive fingerprinting technique, is mainly utilized to identify molecular species and phonon modes of materials. However, direct Raman characterization of two-dimensional materials typically synthesized on catalytic metal substrates is extremely challenging because of the significant electric screening and interfacial electronic couplings. Here, we demonstrate that by covering as-grown graphene with boron nitride (BN) films, the Raman intensity of graphene can be enhanced by two orders of magnitude and is also several times stronger than that of suspended graphene. This great Raman enhancement originates from the optical field amplification by Fabry-Pérot cavity in BN films and the local field plasmon near copper steps. We further demonstrate the direct characterization of the local strain and doping level of as-grown graphene and in situ monitoring of the molecule reaction process by enhanced Raman spectroscopy. Our results will broaden the optical investigations of interfacial sciences on metals, including photoinduced charge transfer dynamics and photocatalysis at metal surfaces.

Light-field focusing and modulation through scattering media based on dual-polarization-encoded digital optical phase conjugation.

Digital optical phase conjugation (DOPC) can be applied for light-field focusing and imaging through or within scattering media. Traditional DOPC only recovers the phase but loses the polarization information of the original incident beam. In this Letter, we propose a dual-polarization-encoded DOPC to recover the full information (both phase and polarization) of the incident beam. The phase distributions of two orthogonal polarization components of the speckle field coming from a multimode fiber are first measured by using digital holography. Then, the phase distributions are separately modulated on two beams and their conjugations are superposed to recover the incident beam through the fiber. By changing the phase difference or amplitude ratio between the two conjugate beams, light fields with complex polarization distribution can also be generated. This method will broaden the application scope of DOPC in imaging through scattering media.

Complete structural characterization of single carbon nanotubes by Rayleigh scattering circular dichroism.

Non-invasive, high-throughput spectroscopic techniques can identify chiral indices (n,m) of carbon nanotubes down to the single-tube level1-6. Yet, for complete characterization and to unlock full functionality, the handedness, the structural property associated with mirror symmetry breaking, also needs to be identified accurately and efficiently7-14. So far, optical methods fail in the handedness characterization of single nanotubes because of the extremely weak chiroptical signals (roughly 10-7) compared with the excitation light15,16. Here we demonstrate the complete structure identification of single nanotubes in terms of both chiral indices and handedness by Rayleigh scattering circular dichroism. Our method is based on the background-free feature of Rayleigh scattering collected at an oblique angle, which enhances the nanotube's chiroptical signal by three to four orders of magnitude compared with conventional absorption circular dichroism. We measured a total of 30 single-walled carbon nanotubes including both semiconducting and metallic nanotubes and found that their absolute chiroptical signals show a distinct structure dependence, which can be qualitatively understood through tight-binding calculations. Our strategy enables the exploration of handedness-related functionality of single nanotubes and provides a facile platform for chiral discrimination and chiral device exploration at the level of individual nanomaterials.

Strain Engineering in Electrochemical Activity and Stability of BiFeO3 Perovskites.

Strain engineering is widely employed to manipulate the intrinsic relationship of activity and the crystal structure, while the mechanism and rational strategy toward high-performance devices are still under investigation. Here straining engineering is utilized to manipulate a series of a typical perovskite structures via introducing different types of heteroions (Bi1-xMxFeO3, M = Ca2+ or Y3+ ion). The space group R3c in BiFeO3 perovskites is found to be maintained with substituting a certain amount of heteroions at Bi3+ sites (<5%), while it would shift into either space groups P4mm (with Ca2+ substitute) or Pnma (with Y3+ substitute) beyond some critical doping amounts (>5%). Such a transformation is linked with the mismatched crystal strain induced by the heteroions substituted at Bi3+ sites, while the activity, stability, and energy storage capability of Bi1-xMxFeO3 have been essentially varied. The results offer a strategy for manipulating stability and activity of perovskites in electrochemical energy conversion and storage.

Development of in situ optical spectroscopy with high temporal resolution in an aberration-corrected transmission electron microscope.

Exploring the corresponding relation between structural and physical properties of materials at the atomic scale remains the fundamental problem in science. With the development of the aberration-corrected transmission electron microscopy (AC-TEM) and the ultrafast optical spectroscopy technique, sub-angstrom-scale spatial resolution and femtosecond-scale temporal resolution can be achieved, respectively. However, the attempt to combine both their advantages is still a great challenge. Here, we develop in situ optical spectroscopy with high temporal resolution in AC-TEM by utilizing a self-designed and manufactured TEM specimen holder, which has the capacity of sub-angstrom-scale spatial resolution and femtosecond-scale temporal resolution. The key and unique design of our apparatus is the use of the fiber bundle, which enables the delivery of focused pulse beams into TEM and collection of optical response simultaneously. The generated focused spot has a size less than 2 µm and can be scanned in plane with an area larger than 75 × 75 µm2. Most importantly, the positive group-velocity dispersion caused by glass fiber is compensated by a pair of diffraction gratings, thus resulting in the generation of pulse beams with a pulse width of about 300 fs (@ 3 mW) in TEM. The in situ experiment, observing the atomic structure of CdSe/ZnS quantum dots in AC-TEM and obtaining the photoluminescence lifetime (∼4.3 ns) in the meantime, has been realized. Further ultrafast optical spectroscopy with femtosecond-scale temporal resolution could be performed in TEM by utilizing this apparatus.

Atomic-scale visualization of metallic lead leak related fine structure in CsPbBr3 quantum dots.

All-inorganic lead halide perovskites (AILHPs) quantum dots (QDs) have been widely investigated as promising materials for optoelectronic applications because of their outstanding luminescence properties. Lead leakage, a common impurity and environmental pollution source that majorly hinders the commercialization of lead halide perovskite devices, has lately attracted considerable attention. Its detrimental influence on the luminescence performance has been widely reported. However, an in-depth experimental study of the chemistry geometry relating to lead leakage in CsPbBr3 QDs has been rarely reported to date. Herein, combining real-time (scanning) transmission electron microscopy ((S)TEM) with density functional theory calculations, we showed detailed atomic and electronic structure study of the phase boundaries in CsPbBr3 QDs during the lead leakage process. A phenomenon of two-phase coexistence was reported to be linked with the lead precipitating in CsPbBr3 QDs. A phase boundary between the Ruddlesden-Popper (RP) phase and conventional orthorhombic perovskite was developed when the lead particle was aggregating in the QDs. Our results suggested that in considering the detrimental exciton quenching process not only the role of lead nanoparticles should be considered but also the influence of the phase boundary on electron-hole transport is worthy of attention. The direct visualization of the delicate atomic and electronic structures associated with lead aggregation in CsPbBr3 sheds light on how the leakage process influences the luminescence performance and provides a potential route for suppressing the generation of environmentally harmful byproducts for advanced devices.

[Analysis of prenatal phenotype and pathogenetic variant in a fetus with Papillorenal syndrome].

OBJECTIVE: To determine the carrier rate of deafness-related genetic variants among 53 873 newborns from Zhengzhou. METHODS: Heel blood samples of the newborns were collected with informed consent from the parents, and 15 loci of 4 genes related to congenital deafness were detected by microarray. RESULTS: In total 2770 newborns were found to carry deafness-related variants, with a carrier rate of 5.142%. 1325 newborns (2.459%) were found to carry heterozygous variants of the GJB2 gene, 1071 (1.988%) were found with SLC26A4 gene variants, 205 were found with GJB3 gene variants (0.381%), and 120 were found with 12S rRNA variants (0.223%). Five newborns have carried homozygous GJB2 variants, two have carried homozygous SLC26A4 variants, five have carried compound heterozygous GJB2 variants, and four have carried compound heterozygous SLC26A4 variants. 33 neonates have carried heterozygous variants of two genes at the same time. CONCLUSION: The carrier rate of deafness-related variants in Zhengzhou, in a declining order, is for GJB2, SLC26A4, GJB3 and 12S rRNA. The common variants included GJB2 235delC and SLC26A4 IVS7-2A>G, which are similar to other regions in China. To carry out genetic screening of neonatal deafness can help to identify congenital, delayed and drug-induced deafness, and initiate treatment and follow-up as early as possible.

Sandwiched graphene/hBN/graphene photonic crystal fibers with high electro-optical modulation depth and speed.

Graphene-photonic crystal fibers (PCFs) are obtained by integrating the broadband optical response and electro-optic tunability of graphene with the high-quality waveguide capacity and easy-integrability of the PCF, and this has been proven to be an important step towards multimaterial multifunctional fiber and all-fiber integrated circuits. However, the reported electro-optic modulator based on directly-grown graphene-PCF suffers from very low response speed (below 100 Hz) due to the slow response of ionic liquid. Here, we propose new functional PCFs with a sandwiched graphene/hBN/graphene (Gr/hBN/Gr) film attached to the hole walls of the fibers, and theoretically demonstrate that the in-line modulator based on it can achieve simultaneous single-mode transmission ranging from 1260 nm to 1700 nm (covering all optical communication bands), significant modulation depth (e.g. ∼42 dB mm-1 at 1550 nm) and high modulation speed (up to ∼0.1 GHz). Furthermore, various device functions can be designed by changing the structure of the fiber, including the length, the hole diameter and the layer numbers of graphene and hBN films. This proposed approach directs a viable path to obtain high-performance all-fiber devices based on hybrid two-dimensional material optical fibers.

Unveiling the Fine Structural Distortion of Atomically Thin Bi2 O2 Se by Third-Harmonic Generation.

Bismuth oxyselenide (Bi2 O2 Se), a new type of 2D material, has recently attracted increased attention due to its robust bandgap, stability under ambient conditions, and ultrahigh electron mobility. In such complex oxides, fine structural distortion tends to play a decisive role in determining the unique physical properties, such as the ferrorotational order, ferroelectricity, and magnetoelasticity. Therefore, an in-depth investigation of the fine structural symmetry of Bi2 O2 Se is necessary to exploit its potential applications. However, conventional techniques are either time consuming or requiring tedious sample treatment. Herein, a noninvasive and high-throughput approach is reported for characterizing the fine structural distortion in 2D centrosymmetric Bi2 O2 Se by polarization-dependent third-harmonic generation (THG). Unprecedentedly, the divergence between the experimental results and the theoretical prediction of the perpendicular component of polarization-dependent THG indicates a fine structural distortion, namely, a <1.4° rotation of the oxygen square in the tetragonal (Bi2 O2 ) layers. This rotation breaks the intrinsic mirror symmetry of 2D Bi2 O2 Se, eventually reducing the symmetry from the D4h to the C4h point group. The results demonstrate that THG is highly sensitive to even fine symmetry variations, thereby showing its potential to uncover hidden phase transitions and interacting polarized sublattices in novel 2D material systems.

Structured light beams created through a multimode fiber via virtual Fourier filtering based on digital optical phase conjugation.

Digital optical phase conjugation (DOPC) is a newly developed technique in wavefront shaping to control light propagation through complex media. Currently, DOPC has been demonstrated for the reconstruction of two- and three-dimensional targets and enabled important applications in many areas. Nevertheless, the reconstruction results are only phase conjugated to the original input targets. Herein, we demonstrate that DOPC could be further developed for creating structured light beams through a multimode fiber (MMF). By applying annular filtering in the virtual Fourier domain of the acquired speckle field, we realize the creation of the quasi-Bessel and donut beams through the MMF. In principle, arbitrary amplitude and/or phase circular symmetry filtering could be performed in the Fourier domain, thus generating the corresponding point spread functions. We expect that the reported technique can be useful for super-resolution endoscopic imaging and optical manipulation through MMFs.

Measurement of full polarization states with hybrid holography based on geometric phase.

We propose a method for measuring the full polarization states of a light field by using hybrid polarization-angular multiplexing digital holography based on geometric phase. Through acquiring the geometric phase distribution of the whole light field by only recording a composite hologram, and according to quantitative relationship between the geometric phase and polarization state, the Stokes parameters of a light field can be calculated. Compared with other methods, this method can be used to obtain the complex amplitude information of the light field simultaneously without requiring other complex devices or elements to be adjusted, thus enabling dynamic polarization state measurement. The measurement results of the light fields generated by standard polarized optical elements, vortex half-wave retarder, and liquid crystal depolarizer verified this method's feasibility and validity.

Effects of iron spin transition on the electronic structure, thermal expansivity and lattice thermal conductivity of ferropericlase: a first principles study.

The effects of the spin transition on the electronic structure, thermal expansivity and lattice thermal conductivity of ferropericlase are studied by first principles calculations at high pressures. The electronic structures indicate that ferropericlase is an insulator for high-spin and low-spin states. Combined with the quasiharmonic approximation, our calculations show that the thermal expansivity is larger in the high-spin state than in the low-spin state at ambient pressure, while the magnitude exhibits a crossover between high-spin and low-spin with increasing pressure. The calculated lattice thermal conductivity exhibits a drastic reduction upon the inclusion of ferrous iron, which is consistent with previous experimental studies. However, a subsequent enhancement in the thermal conductivity is obtained, which is associated with the spin transition. Mechanisms are discussed for the variation in thermal conductivity by the inclusion of ferrous iron and the spin transition.

Ca2+ complexation of dissolved organic matter in arid inland lakes is significantly affected by drastic seasonal change of salinity.

CaCO3 precipitation is one of the most common and important geochemical processes in the arid inland waters and it can be significantly affected by interaction of DOM with Ca2+. Effects of the drastic seasonal change of water salinity on interaction of DOM with Ca2+ in the arid inland waters were completely unknown. In the present study, complexation of DOM with Ca2+ in the freshwater (0.5‰ salinity) and hypersaline water (70‰ salinity) were comparatively examined by excitation-emission matrix (EEM) fluorescence quenching titration and isothermal titration calorimetry (ITC). The complexation of DOM with Ca2+ was significantly influenced by the drastic change of salinity. The ITC complexation is exothermic at 0.5‰ salinity but turns to an endothermic process at 70‰ salinity. More energy is needed for the complex reaction between DOM and Ca2+ under the hypersaline condition than in the fresh water. Fluorescence quenching titration indicates that DOM has stronger binding ability toward Ca2+ in the freshwater than in the saline water, and more fractions of DOM in the freshwater are accessible to Ca2+ than in the saline water. Ca2+ complexation in the DOM is dominated by the tryptophan-like components at both salinities and the complexation of Ca2+ with fulvic acid-like components is ignorable. The findings is important for understanding the aquatic geochemical processes in some lakes that seriously affected by irrigation water use in the arid zone.

Integrated digital holographic microscopy based on surface plasmon resonance.

We propose a novel digital holographic microscopy (DHM) by integrating surface plasmon holographic microscopy (SPHM) with reflection DHM based on the angular and polarization multiplexing techniques. Taking advantages of the high sensitivity of surface plasmon resonance (SPR) and the high reflectivity of gold film, the tiny variations of specimen's refractive index (RI) can be measured by using SPHM, and meanwhile, the thickness changes of the specimen can be determined by means of reflection DHM. We experimentally monitor the volatilization process of an alcohol-water mixture droplet to verify the validity of the integrated DHM. The proposed microscopy is very promising in the objective-coupling SPR microscopy for multi-information measurements of diverse specimens with low-contrast RI distributions (biomolecules, nanofluids, etc.) in a dynamic and nondestructive way.

Measurement of ultrafast combustion process of premixed ethylene/oxygen flames in narrow channel with digital holographic interferometry.

The premixed ethylene and oxygen flame that is burning in a narrow channel is investigated with digital holographic interferometry (DHI). Combustion in either a narrow tube or channel is quite different. This is caused by the significant effects of the boundary layer. The flame's acceleration rate will be enhanced as the tube diameter decreases. Usually, flame and shock wave propagation, which occurs during the premixed ethylene/oxygen flame combustion in the measurement area, is less than few milliseconds, so that general camera can rarely capture this fast event. This paper demonstrates that, by introducing the high-speed camera to DHI, the propagation of weak compression wave, flame, and shock wave generated in the narrow channel is successfully measured with a temporal resolution of 10 µs. The ultrafast processes of the flame front changing, as well as the shock wave coupling and separating, are clearly shown from the reconstructed phase distributions of the recorded holograms; corresponding density variations are simultaneously calculated. The results could provide references for the micro-scale propulsion and power devices design and use, and this proposed configuration can also easily adapt to other kinds of ultrafast processes in fluids.

Reconstruction of structured laser beams through a multimode fiber based on digital optical phase conjugation.

The digital optical phase conjugation (DOPC) technique is being actively developed for optical focusing and imaging through or inside complex media. Due to its time-reversal nature, DOPC has been exploited to regenerate different intensity targets. However, whether the targets with three-dimensional information through complex media could be recovered has not been experimentally demonstrated, to the best of our knowledge. Here, we present a method to regenerate structured laser beams based on DOPC. Although only the phase of the original scattered wave is time reversed, the reconstruction of a quasi-Bessel beam and vortex beams through a multimode fiber (MMF) is demonstrated. The regenerated quasi-Bessel beam shows the features of sub-diffraction focusing and a longer depth of field with respect to a Gaussian beam. Moreover, the reconstruction of vortex beams shows the fidelity of DOPC both in amplitude and phase, which is demonstrated for the first time, to the best of our knowledge. We also prove that the reconstruction results of DOPC through the MMF are indeed phase conjugate to the original targets. We expect that these results could be useful in super-resolution imaging and optical micromanipulation through complex media, and further pave the way for achieving three-dimensional imaging based on DOPC.

Wavelength-multiplexing surface plasmon holographic microscopy.

Surface plasmon holographic microscopy (SPHM), which combines surface plasmon microscopy with digital holographic microscopy, can be applied for amplitude- and phase-contrast surface plasmon resonance (SPR) imaging. In this paper, we propose an improved SPHM with the wavelength multiplexing technique based on two laser sources and a common-path hologram recording configuration. Through recording and reconstructing the SPR images at two wavelengths simultaneously employing the improved SPHM, tiny variation of dielectric refractive index in near field is quantitatively monitored with an extended measurement range while maintaining the high sensitivity. Moreover, imaging onion tissues is performed to demonstrate that the detection sensitivities of two wavelengths can compensate for each other in SPR imaging. The proposed wavelength-multiplexing SPHM presents simple structure, high temporal stability and inherent capability of phase curvature compensation, as well as shows great potentials for further applications in monitoring diverse dynamic processes related with refractive index variations and imaging biological tissues with low-contrast refractive index distributions in the near field.