Spontaneous formation of multilayer refractory carbide coatings in a molten salt media.

Refractory materials hold great promise to develop functional multilayer coating for extreme environments and temperature applications but require high temperature and complex synthesis to overcome their strong atomic bonding and form a multilayer structure. Here, a spontaneous reaction producing sophisticated multilayer refractory carbide coatings on carbon fiber (CF) is reported. This approach utilizes a relatively low-temperature (950 °C) molten-salt process for forming refractory carbides. The reaction of titanium (Ti), chromium (Cr), and CF yields a complex, high-quality multilayer carbide coating composed of 1) Cr carbide (Cr3C2), 2) Ti carbide, and 3) Cr3C2 layers. The layered sequence arises from a difference in metal dissolutions, reactions, and diffusion rates in the salt media. The multilayer-coated CFs act as a permeable oxidation barrier with no crystalline degradation of the CFs after extreme temperature (1,200 °C) and environment (oxyacetylene flame) exposure. The synthesis of high-quality multilayer refractory coating in a fast, efficient, easy, and clean manner may answer the need for industrial applications that develop cheap and reliable extreme environment protection barriers.

Self-absorption reduction in laser-induced breakdown spectroscopy using laser-stimulated absorption: publisher's note.

This publisher's note contains corrections to Opt. Lett.40, 5224 (2015).OPLEDP0146-959210.1364/OL.40.005224.

Diagnosis of nasopharyngeal carcinoma from serum samples using hyperspectral imaging combined with a chemometric method.

Diagnosing nasopharyngeal carcinoma (NPC) is a significant challenge because of the highly complex process. We proposed an approach to diagnose NPC serum using a combination of hyperspectral imaging and weight-based principal component analysis. Samples were prepared by pressing boric acid into pellets for use as the sera substrate. The sera, collected from 100 healthy volunteers and 60 NPC patients, was dripped onto the surface of the substrate for hyperspectral imaging. The characteristic spectral bands were selected based on the variable weight obtained from a support vector machine (SVM) model, using principal component analysis (PCA) to reduce the dimension in the extracted bands. Obtained results show that the accuracy rate, sensitivity, and specificity between the NPC sera and the sera of the healthy controls reached extremely high levels of 99.15%, 98.79%, and 99.36%, respectively. For the model's consistency evaluation, we found that the Kappa and area under the curve (AUC) of the receiver operating characteristic (ROC) curve were 0.99 and 0.98, respectively. These results suggest that the developed approach could serve as a noninvasive diagnostic and screening tool for highly accurate and consistent detection of NPC. Hence, a combination of hyperspectral imaging (HSI) and a weighted principal component analysis (WPCA)-SVM model represents a powerful and promising tool for NPC diagnosis.

Accuracy and stability improvement for meat species identification using multiplicative scatter correction and laser-induced breakdown spectroscopy.

An efficient method has been developed to identify meat species by using laser-induced breakdown spectroscopy (LIBS). To improve the accuracy and stability of meat species identification, multiplicative scatter correction (MSC) was adopted to first pretreat the spectrum for correction of spectrum scatter. Then the corrected spectra were identified by using the K-nearest neighbor (KNN) model. The results showed that the identification rate improved from 94.17% to 100% and the prediction coefficient of variance (CV) decreased from 5.16% to 0.56%. This means that the accuracy and stability of meat species identification using MSC and LIBS simultaneously improved. In light of the findings, the proposed method can be a valuable tool for meat species identification using LIBS.

Ultraviolet laser photolysis of hydrocarbons for nondiamond carbon suppression in chemical vapor deposition of diamond films.

In this work, we demonstrate that ultraviolet (UV) laser photolysis of hydrocarbon species alters the flame chemistry such that it promotes the diamond growth rate and film quality. Optical emission spectroscopy and laser-induced fluorescence demonstrate that direct UV laser irradiation of a diamond-forming combustion flame produces a large amount of reactive species that play critical roles in diamond growth, thereby leading to enhanced diamond growth. The diamond growth rate is more than doubled, and diamond quality is improved by 4.2%. Investigation of the diamond nucleation process suggests that the diamond nucleation time is significantly shortened and nondiamond carbon accumulation is greatly suppressed with UV laser irradiation of the combustion flame in a laser-parallel-to-substrate geometry. A narrow amorphous carbon transition zone, averaging 4 nm in thickness, is identified at the film-substrate interface area using transmission electron microscopy, confirming the suppression effect of UV laser irradiation on nondiamond carbon formation. The discovery of the advantages of UV photochemistry in diamond growth is of great significance for vastly improving the synthesis of a broad range of technically important materials.

Electrons dynamics control by shaping femtosecond laser pulses in micro/nanofabrication: modeling, method, measurement and application.

During femtosecond laser fabrication, photons are mainly absorbed by electrons, and the subsequent energy transfer from electrons to ions is of picosecond order. Hence, lattice motion is negligible within the femtosecond pulse duration, whereas femtosecond photon-electron interactions dominate the entire fabrication process. Therefore, femtosecond laser fabrication must be improved by controlling localized transient electron dynamics, which poses a challenge for measuring and controlling at the electron level during fabrication processes. Pump-probe spectroscopy presents a viable solution, which can be used to observe electron dynamics during a chemical reaction. In fact, femtosecond pulse durations are shorter than many physical/chemical characteristic times, which permits manipulating, adjusting, or interfering with electron dynamics. Hence, we proposed to control localized transient electron dynamics by temporally or spatially shaping femtosecond pulses, and further to modify localized transient materials properties, and then to adjust material phase change, and eventually to implement a novel fabrication method. This review covers our progresses over the past decade regarding electrons dynamics control (EDC) by shaping femtosecond laser pulses in micro/nanomanufacturing: (1) Theoretical models were developed to prove EDC feasibility and reveal its mechanisms; (2) on the basis of the theoretical predictions, many experiments are conducted to validate our EDC-based femtosecond laser fabrication method. Seven examples are reported, which proves that the proposed method can significantly improve fabrication precision, quality, throughput and repeatability and effectively control micro/nanoscale structures; (3) a multiscale measurement system was proposed and developed to study the fundamentals of EDC from the femtosecond scale to the nanosecond scale and to the millisecond scale; and (4) As an example of practical applications, our method was employed to fabricate some key structures in one of the 16 Chinese National S&T Major Projects, for which electron dynamics were measured using our multiscale measurement system.

Rainbow peacock spiders inspire miniature super-iridescent optics.

Colour produced by wavelength-dependent light scattering is a key component of visual communication in nature and acts particularly strongly in visual signalling by structurally-coloured animals during courtship. Two miniature peacock spiders (Maratus robinsoni and M. chrysomelas) court females using tiny structured scales (~ 40 × 10 µm2) that reflect the full visual spectrum. Using TEM and optical modelling, we show that the spiders' scales have 2D nanogratings on microscale 3D convex surfaces with at least twice the resolving power of a conventional 2D diffraction grating of the same period. Whereas the long optical path lengths required for light-dispersive components to resolve individual wavelengths constrain current spectrometers to bulky sizes, our nano-3D printed prototypes demonstrate that the design principle of the peacock spiders' scales could inspire novel, miniature light-dispersive components.

Thermally Stable and Electrically Conductive, Vertically Aligned Carbon Nanotube/Silicon Infiltrated Composite Structures for High-Temperature Electrodes.

Traditional ceramic-based, high-temperature electrode materials (e.g., lanthanum chromate) are severely limited due to their conditional electrical conductivity and poor stability under harsh circumstances. Advanced composite structures based on vertically aligned carbon nanotubes (VACNTs) and high-temperature ceramics are expected to address this grand challenge, in which ceramic serves as a shielding layer protecting the VACNTs from the oxidation and erosive environment, while the VACNTs work as a conductor. However, it is still a great challenge to fabricate VACNT/ceramic composite structures due to the limited diffusion of ceramics inside the VACNT arrays. In this work, we report on the controllable fabrication of infiltrated (and noninfiltrated) VACNT/silicon composite structures via thermal chemical vapor deposition (CVD) [and laser-assisted CVD]. In laser-assisted CVD, low-crystalline silicon (Si) was quickly deposited at the VACNT subsurfaces/surfaces followed by the formation of high-crystalline Si layers, thus resulting in noninfiltrated composite structures. Unlike laser-assisted CVD, thermal CVD activated the precursors inside and outside the VACNTs simultaneously, which realized uniform infiltrated VACNT/Si composite structures. The growth mechanisms for infiltrated and noninfiltrated VACNT/ceramic composites, which we attributed to the different temperature distributions and gas diffusion mechanism in VACNTs, were investigated. More importantly, the as-farbicated composite structures exhibited excellent multifunctional properties, such as excellent antioxidative ability (up to 1100 °C), high thermal stability (up to 1400 °C), good high velocity hot gas erosion resistance, and good electrical conductivity (∼8.95 Sm-1 at 823 K). The work presented here brings a simple, new approach to the fabrication of advanced composite structures for hot electrode applications.

Formation of curved nanostructures on lithium niobate surfaces using femtosecond laser pulses.

Curved nanostructures are formed on the lithium niobate surfaces after irradiation with linearly polarized femtosecond laser pulses. It is shown that the curvature of nanostructures critically depends on the overlapping of two successive pulses, which can be controlled by changing the scanning speed or scanning direction of the laser. Electrical field simulation using the finite-difference time-domain (FDTD) method indicates that the electric field is locally enhanced at the crater edge when a focused pulse propagates through an elliptical crater produced by the previous pulse, which is responsible for the formation of the curved nanostructures. From the experimental and simulation results, the formation mechanism of the curved nanostructures is presented.

Fast Growth of GaN Epilayers via Laser-Assisted Metal-Organic Chemical Vapor Deposition for Ultraviolet Photodetector Applications.

In this study, we successfully developed a carbon dioxide (CO2)-laser-assisted metal-organic chemical vapor deposition (LMOCVD) approach to fast synthesis of high-quality gallium nitride (GaN) epilayers on Al2O3 [sapphire(0001)] substrates. By employing a two-step growth procedure, high crystallinity and smooth GaN epilayers with a fast growth rate of 25.8 µm/h were obtained. The high crystallinity was confirmed by a combination of techniques, including X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and atomic force microscopy. By optimizing growth parameters, the ∼4.3-µm-thick GaN films grown at 990 °C for 10 min showed a smooth surface with a root-mean-square surface roughness of ∼1.9 nm and excellent thickness uniformity with sharp GaN/substrate interfaces. The full-width at half-maximum values of the GaN(0002) X-ray rocking curve of 313 arcsec and the GaN(101̅2) X-ray rocking curve of 390 arcsec further confirmed the high crystallinity of the GaN epilayers. We also fabricated ultraviolet (UV) photodetectors based on the as-grown GaN layers, which exhibited a high responsivity of 0.108 A W-1 at 367 nm and a fast response time of ∼125 ns, demonstrating its high optical quality with potential in optoelectronic applications. Our strategy thus provides a simple and cost-effective means toward fast and high-quality GaN heteroepitaxy growth suitable for fabricating high-performance GaN-based UV detectors.

A series of pure-blue-light emitting Cu(i) complexes with thermally activated delayed fluorescence: structural, photophysical, and computational studies.

Four mononuclear Cu(i)-halide complexes containing phosphines and pyridine ligands with strong electron donor substituents, [CuCl(PPh3)2(4-NMe2py)] (1), [CuI(PPh3)2(4-NH2py)] (2), [CuI(POP)(4-NH2py)] (3), and [CuI(POP)(4-NMe2py)]·0.5(Et2O) (4), (PPh3 = triphenylphosphine, 4-NMe2py = 4-(dimethylamino)pyridine, POP = bis[(2-diphenyl-phosphino)phenyl]ether, 4-NH2py = 4-aminopyridine, Et2O = diethyl ether) were synthesized and studied with regard to their structural, photophysical properties and theoretical calculations. The complexes exhibit pure blue thermally activated delayed fluorescence (λmax = 442 (1), 436 (2), 464 (3), and 448 nm (4)) in crystalline at room temperature. Emission lifetime analyses and density functional theory (DFT) calculations show that the blue-light emission at room temperature is the singlet (metal + halide)-to-ligand charge transfer state, (1(M + X)LCT), while that at 77 K is the state of 3(M + X)LCT transition character, owing to the small singlet-triplet energy gaps (ΔE = 660-1680 cm-1). X-ray diffraction structure analysis, photophysical studies and theoretical calculations suggest that the much larger torsion angle between the N-heterocyclic rings and N-Cu-X planes of complex 3 than that of 1, 2 and 4 might causes the bathochromic shift of luminescence, although these complexes containing similar heterocycle ligands.

An ab initio study of the nickel-catalyzed transformation of amorphous carbon into graphene in rapid thermal processing.

Ab initio molecular dynamics (AIMD) simulations are employed to investigate the chemical mechanism underlying the Ni-catalyzed transformation of amorphous carbon (a-C) into graphene in the rapid thermal processing (RTP) experiment to directly grow graphene on various dielectric surfaces via the evaporation of surplus Ni and C at 1100 °C (below the melting point of bulk Ni). It is found that the a-C-to-graphene transformation entails the metal-induced crystallization and layer exchange mechanism, rather than the conventional dissolution/precipitation mechanism typically involved in Ni-catalyzed chemical vapor deposition (CVD) growth of graphene. The multi-layer graphene can be tuned by changing the relative thicknesses of deposited a-C and Ni thin films. Our AIMD simulations suggest that the easy evaporation of surplus Ni with excess C is likely attributed to the formation of a viscous-liquid-like Ni-C solution within the temperature range of 900-1800 K and to the faster diffusion of C atoms than that of Ni atoms above 600 K. Even at room temperature, sp(3)-C atoms in a-C are quickly converted to sp(2)-C atoms in the course of the simulation, and the graphitic C formation can occur at low temperature. When the temperature is as high as 1200 K, the grown graphitic structures reversely dissolve into Ni. Because the rate of temperature increase is considerably faster in the AIMD simulations than in realistic experiments, defects in the grown graphitic structures are kinetically trapped. In this kinetic growth stage, the carbon structures grown from sp(3)-carbon or from sp(2)-carbon exhibit marked differences.

Laser-Directed Assembly of Aligned Carbon Nanotubes in Three Dimensions for Multifunctional Device Fabrication.

Laser-directed assembly of multiwalled carbon nanotubes (MWNTs) in 3D space is investigated via a two-photon polymerization technique. MWNT-thiol-acrylate (MTA) composite resins are developed with high MWNT concentrations up to 0.2 wt%, over one order of magnitude higher than previously published work. Significantly enhanced electrical and mechanical properties of the 3D micro-/nanostructures are achieved. Microelectronic devices made of the MTA resins are demonstrated.

[Mapping Applications in Laser-Induced Breakdown Spectroscopy].

LIBS mapping was used to analyze and detect the elemental distribution of iron ore surface with self-developed software and 532 nm Nd∶YAG laser. Firstly, in order to illustrate the relationship between element content and spectral intensity, the calibration curve was established by scanning the surface of standard sample. Then, a self-made sample was homogeneously divided into three parts that was pressed by three different standard iron ore powders. For the purpose of validating the mapping technology, a two-dimensional concentration distribution profile was generated after scanning the sample surface which was compared with surface morphology phase of the sample. Finally, with the resolution of 100 microns, the surface scanning analysis of the natural iron ore within the scope of 14 mm×11 mm was implemented. With this basis, the distribution profile of the elements Ca, Al, Ti and Mn were obtained, and the analysis results were compared with the surface morphology phase of the natural iron ore. The results showed that LIBS mapping technology could be used to achieve the qualitative analysis of component gradient distribution of the heterogeneous sample surface.

Self-absorption reduction in laser-induced breakdown spectroscopy using laser-stimulated absorption.

The self-absorption effect is one of the main bottlenecks for the laser-induced breakdown spectroscopy (LIBS) technique. In this Letter, LIBS assisted by laser-stimulated absorption (LSA-LIBS) is proposed to solve this problem. The process of LSA in self-absorption reduction is discussed and confirmed. The serious self-absorption phenomena of spectral lines (K, Mn, and Al) were not observed in LSA-LIBS. The full width at half-maximum (FWHM) of K, Mn, and Al was reduced by about 58%, 25%, and 52%, respectively. The results demonstrate the capability of this approach to self-absorption reduction in the LIBS technique.

[Research Progress on Laser-Induced Breakdown Spectroscopy Based on Resonance Excitation].

Laser-induced breakdown spectroscopy (LIBS), a new kind of atomic spectrum analysis technology, has attracted much atterition of the researchers due to its characteristics of real-time, simultaneous multi-element analysis, and no sample preparation. However, the poor analytical sensitivity has been an important factor that restricts the development of this technology. LIBS based on resonance excitation combines atomic fluorescence spectroscopy and laser-induced breakdown spectroscopy and selectively excites the target elements. In this way, the analytical sensitivity of LIBS can be improved substantially and its application for trace elements detection is greatly expanded. In this paper, the research development of LIBS based on resonance excitation is summarized. The generation of atomic, fluorescence spectrum in laser-induced plasma, the typical classification and the basic principle of LIBS based on resonance. excitation are introduced. The influence of ablation laser energy, resonant laser energy and wavelength, delay between the ablation laser and the resonant laser, and the gate width on spectral enhancement are analyzed in detail. The application status and deficiencies of LIBS based on resonance excitation in the fields of metallurgy, environmental monitoring and isotope detection are elaborated. Future prospects of LIBS based on resonance excitation are also described.

Surface-enhanced Raman spectral biomarkers correlate with Ankle Brachial Index and characterize leg muscle biochemical composition of patients with peripheral arterial disease.

Peripheral arterial disease (PAD) is characterized by atherosclerotic blockages of the arteries supplying the lower extremities, which cause a progressive accumulation of ischemic injury to the skeletal muscles of the lower limbs. This injury includes altered metabolic processes, damaged organelles, and compromised bioenergetics in the affected muscles. The objective of this study was to explore the association of Raman spectral signatures of muscle biochemistry with the severity of atherosclerosis in the legs as determined by the Ankle Brachial Index (ABI) and clinical presentation. We collected muscle biopsies from the gastrocnemius (calf muscle) of five patients with clinically diagnosed claudication, five patients with clinically diagnosed critical limb ischemia (CLI), and five control patients who did not have PAD. A partial least squares regression (PLSR) model was able to predict patient ABI with a correlation coefficient of 0.99 during training and a correlation coefficient of 0.85 using a full cross-validation. When using the first three PLS factor scores in combination with linear discriminant analysis, the discriminant model was able to correctly classify the control, claudicating, and CLI patients with 100% accuracy, using a full cross-validation procedure. Raman spectroscopy is capable of detecting and measuring unique biochemical signatures of skeletal muscle. These signatures can discriminate control muscles from PAD muscles and correlate with the ABI and clinical presentation of the PAD patient. Raman spectroscopy provides novel spectral biomarkers that may complement existing methods for diagnosis and monitoring treatment of PAD patients.

Two-photon polymerization: investigation of chemical and mechanical properties of resins using Raman microspectroscopy.

In this study, the degree of conversion (DC) of an acrylic-based resin (IP-L 780) in two-photon polymerization (TPP) is systematically investigated via Raman microspectroscopy. A quantitative relationship between TPP laser parameters and the DC of the resin is established. Nonlinear increase in DC with increased laser average power is observed. The resin DC is more sensitive to the laser average power than the laser writing speed. Nanoindentation was employed to correlate the results obtained from Raman microspectroscopy with the mechanical properties of microstructures fabricated by TPP. At constant writing speeds, microstructures fabricated with high laser average powers possess high hardness and high reduced Young's modulus (RYM), indicating high DCs. The results are in line with high DCs measured under the same TPP parameters in Raman microspectroscopy. Raman microspectroscopy is proved to be an effective, rapid, and nondestructive method characterizing microstructures fabrication by TPP.

Direct writing of graphene patterns on insulating substrates under ambient conditions.

To unleash the full potential of graphene in electronics and optoelectronics, high-quality graphene patterns on insulating substrates are required. However, existing methods generally follow a "synthesis + patterning" strategy, which are time consuming and costly for fabricating high-quality graphene patterns on desired substrates. We developed a nanofabrication process to deposit high-quality graphene patterns directly on insulating substrates via a solid-phase laser direct writing (LDW) process. Open-air and room-temperature fabrication of graphene patterns on insulating substrates has been achieved via a femtosecond LDW process without graphene transfer and patterning. Various graphene patterns, including texts, spirals, line arrays, and integrated circuit patterns, with a feature line width of 800 nm and a low sheet resistance of 205 ohm/sq, were fabricated. The LDW method provides a facile and cost-effective way to fabricate complex and high-quality graphene patterns directly on target substrates, which opens a door for fabricating various advanced functional devices.

Control of crystallographic orientation in diamond synthesis through laser resonant vibrational excitation of precursor molecules.

Crystallographic orientations determine the optical, electrical, mechanical, and thermal properties of crystals. Control of crystallographic orientations has been studied by changing the growth parameters, including temperature, pressure, proportion of precursors, and surface conditions. However, molecular dynamic mechanisms underlying these controls remain largely unknown. Here we achieved control of crystallographic orientations in diamond growth through a joint experimental and theoretical study of laser resonant vibrational excitation of precursor molecules (ethylene). Resonant vibrational excitation of the ethylene molecules using a wavelength-tunable CO2 laser steers the chemical reactions and promotes proportion of intermediate oxide species, which results in preferential growth of {100}-oriented diamond films and diamond single crystals in open air. Quantum molecular dynamic simulations and calculations of chemisorption energies of radicals detected from our mass-spectroscopy experiment provide an in-depth understanding of molecular reaction mechanisms in the steering of chemical reactions and control of crystallographic orientations. This finding opens up a new avenue for controlled chemical vapor deposition of crystals through resonant vibrational excitations to steer surface chemistry.