Crystal Thickness Research Articles

A novel approach for preparation of nanocomposites with an excellent rigidity/deformability balance based on reinforced HDPE with halloysite

An innovative approach, designated as supported activator (SA), allows preparation of high density polyethylene (HDPE)-based highly performant hybrid materials. This procedure makes use of a nano-sized supported methylaluminoxane (MAO)-activator, based on halloysite natural nanotubes (HNT), combined with an in situ supporting concept. The new protocol when compared with a more conventional approach gives rise to higher polymerization activities as well as ultimate materials with better morphological features, greater crystallinity, thicker crystals, and highly increased stiffness. Moreover, a remarkable synergy between rigidity and toughness is attained. The Young’s modulus of a film obtained from the nanocomposite with the highest HNT content increases more than 70 % relatively to a pristine HDPE film, while retaining the limit stretching ability of pristine HDPE (more than 800%). A beneficial impact of using a high aspect ratio support such as HNT in the mechanical properties is also observed, when compared to similar HDPE hybrid materials derived from dendrimer-like silica (DS) nanospheres. Interestingly, polymerization activity, polymer features and derived properties found in the ultimate materials are less impacted by support/filler nature than by preparation method. This fact highlights the crucial role of the synthetic methodology used and corroborates the high potential of the SA route for the preparation of high-performance polyethylene-based nanocomposites with an excellent balance between stiffness and deformability.

Low coercivity magnetoplasmonic crystal based on a thin permalloy film for magnetic field sensing applications

This research is devoted to the fabrication of 5-nm thick permalloy film-based magnetoplasmonic crystal for magnetic field sensing applications. Optical and magneto-optical activity of the magnetoplasmonic crystal is studied with the means of numerical modeling and spectroscopy techniques. The studied sample achieves sensitivity to an external DC magnetic field of 7.5 mOe in the 5.1 Oe required modulation AC magnetic field. Obtained experimental and modeling results can be used for the fabrication of cheaper and more energy-efficient sensing elements for magnetoplasmonic crystal-based magnetic field sensors due to the reduction of required ferromagnetic material and modulation magnetic field.

High-quality micropore drilling by using orthogonally polarized femtosecond double-pulse bursts

The present study proposes a facile method for fabricating high-quality, high-precision, and small-taper micropores. An YVO4 crystal is used to split a single pulse into two sub-pulses with perpendicular polarization, and the pulse delay is adjusted by controlling the crystal's thickness. The femtosecond double-pulse bursts can enhance the ablation, and the maximum ablation efficiency is achieved when the pulse delay is 4 ps. The two-temperature model revealed that the ablation can be enhanced by enhancing electron-phonon coupling and decreasing the electron thermal conductivity when changing the pulse delay. The orthogonally polarized femtosecond double-pulse bursts eliminate the polarization removal caused by the reflectivity difference between p- and s-polarized light, improving the uniformity of the micropore sidewall and the consistency of the inlet and outlet. The mechanism underlying defect formation and the relationship between the processing parameters and heat accumulation were systematically investigated. Elemental composition and phase analyses indicated that femtosecond double-pulse bursts had negligible adverse effects on samples. The proposed facile method can be used to drill high-quality micropores in various industrial applications.

Disentangling multiple scattering with deep learning: application to strain mapping from electron diffraction patterns

A fast, robust pipeline for strain mapping of crystalline materials is important for many technological applications. Scanning electron nanodiffraction allows us to calculate strain maps with high accuracy and spatial resolutions, but this technique is limited when the electron beam undergoes multiple scattering. Deep-learning methods have the potential to invert these complex signals, but require a large number of training examples. We implement a Fourier space, complex-valued deep-neural network, FCU-Net, to invert highly nonlinear electron diffraction patterns into the corresponding quantitative structure factor images. FCU-Net was trained using over 200,000 unique simulated dynamical diffraction patterns from different combinations of crystal structures, orientations, thicknesses, and microscope parameters, which are augmented with experimental artifacts. We evaluated FCU-Net against simulated and experimental datasets, where it substantially outperforms conventional analysis methods. Our code, models, and training library are open-source and may be adapted to different diffraction measurement problems.

Anisotropic spatial entanglement

The photon pairs generated through spontaneous parametric down-conversion (SPDC) possess strong correlations in their transverse position and momentum degrees of freedom. For such photon pairs, the transverse position correlation length depends on the crystal thickness and the pump wavelength. In contrast, the transverse momentum correlation length depends on the pump's beam waist and spatial coherence length. By controlling these parameters, it is possible to engineer spatial entanglement. Here, we utilize the circular asymmetry of the pump by using an elliptical-Gaussian beam to change the degree of entanglement in transverse directions, which we call anisotropic entanglement. We show the interrelation between the degree of anisotropic entanglement and the asymmetry in the beam width. In addition, we also show that for a highly asymmetric pump beam, the entanglement vanishes along the direction of the thinner beam width, while it remains intact in the direction of the broader beam width.

Broadband THz wave generation in organic benzothiazolium crystals at MHz repetition rates [Invited

We present broadband terahertz wave generation based on benzothiazolium crystals at a 100 MHz repetition rate. Among various benzothiazolium crystals, we chose PMB-4TFS (2-(4-(4-(hydroxymethyl)piperidin-1-yl)styryl)-3-methylbenzothiazol-3-ium 4-(trifluorome-thyl)benzenesulfonate) due to its large macroscopic optical nonlinearity, good crystal characteristics, and suppressed molecular phonon vibrations. When pumped at the telecommunication wavelength of 1560 nm, the generated THz spectrum covers up to ∼15 THz and the corresponding THz amplitude for a 0.29 mm thick crystal at normal incidence is by more than one order of magnitude higher compared to the inorganic standard, 1.0 mm thick ZnTe generator crystal.

Synthesis of Self-Assembled Single Atomic Layer Gold Crystals-Goldene.

We report, for the first time, a technique to synthesize free-standing, one-atom thick 2D gold crystals (namely, goldene) and self-assembled 2D periodic arrays of goldene. High-resolution transmission electron microscopy (HRTEM) imaging of goldene revealed herringbone and honeycomb lattices, which are primarily gold surface features due to its reconstruction. Imaging of these surface-only features by a nonsurface characterization technique such as HRTEM is an unequivocal proof of the absence of three-dimensionality in goldene. Atomic force microscopy confirmed 1-2 Å thickness of goldene. High-resolution X-ray photoelectron spectroscopy (HR-XPS), selective area electron diffraction, and energy-dispersive X-ray spectroscopy confirmed the chemical identity of goldene. We discovered the phenomenon of electric field-induced self-assembly of goldene supracrystals with a herringbone structure and developed an electric field printing (e-print) technique for goldene arrays. Goldene showed a semiconductor response with a knee voltage of ∼3.2 V, and I/V spectroscopy revealed periodic room temperature Coulomb blockade oscillations. These observations are consistent with the theoretical calculations reported in the literature predicting enhanced Coulombic interactions between gold valence electrons and the nucleus in stable 2D gold. Goldene exhibited multiple, intense, and well-resolved optical absorption peaks and several fine bands across the UV-vis region, and we calculated its optical band gap to be 3.59 eV. Magnetic force microscopy measurements of goldene periodic arrays showed a ∼5 mV peak amplitude confirming its ferromagnetism. Optical and magnetic properties of goldene are consistent with those reported in the literature for 2D planar gold clusters with less than 12 atoms.

Exploring the effect of dielectric screening on neutral and charged-exciton properties in monolayer and bilayer MoTe2

Dielectric engineering of heterostructures made from two-dimensional van der Waals semiconductors is a unique and powerful tool to tailor the electric and optical band gaps solely via the dielectric environment and the crystal thickness modulation. Here, we utilize high quality MoTe2 monolayer and bilayer crystals as a candidate for near-infrared photonic applications. The crystals are exfoliated on various technologically relevant carrier substrates: silicon/silicon dioxide, poly(methyl methacrylate), hexagonal boron nitride, silicon carbide, and silicon nitride. These substrates provide a large range of high frequency dielectric constants from 2.1 to 7.0 for MoTe2-containing heterostructures. We assess the relationship between the environmental dielectric function and Coulomb screening by combining detailed spectroscopic measurements, utilizing low-temperature and high-spatially resolved photoluminescence and contrast reflectivity, with microscopic many-body modeling, to explore the potential of this less-recognized material platform for applications in optoelectronics at photon wavelengths above 1 μm. We observe a redshift of the optical gap emission energy from the monolayer to bilayer regime on the order of 30 meV. Furthermore, the thickness controlled shift is slightly larger than the one induced by the local dielectric environment, which ranges on the order of 20 meV for the MoTe2 monolayers and on the order of 8 meV for the MoTe2 bilayers. We also show that the local dielectric screening barely affects the trion binding energy, which is captured by our microscopic model, accounting for the screened Coulomb potential for the heterostructures.

Linseed oil supplementation and DGAT1 K232A polymorphism affect the triacylglycerol composition and crystallization of milk fat

We studied the effect of dietary linseed oil (LSO) supplementation and DGAT1 K232A (DGAT1) polymorphism on the triacylglycerol composition and crystallization of bovine milk fat. LSO supplementation increased unsaturated triacylglycerols, notably in the C52–C54 carbon range, while reducing the saturated C29–C49 triacylglycerols. These changes were associated with an increase in the low-melting fraction and the crystal lamellar thickness, as well as a reduction in the medium and high-melting fractions and the formation of the most abundant crystal type at 20 °C (β’-2 polymorph). Furthermore, DGAT1 KK was associated with higher levels of odd-chain saturated triacylglycerols than DGAT1 AA, and it was also associated with an increase in the high-melting fraction and the endset melting temperature. An interaction between diet and DGAT1 for the unsaturated C54 triacylglycerols accentuated the effects of LSO supplementation with DGAT1 AA. These findings show that genetic polymorphism and cows’ diet can have considerable effects on milk fat properties.

Scalable microstructured semiconductor THz pulse sources.

In recent years several microstructured lithium niobate THz pulse source were suggested for high-energy applications. Two types of those, the reflective and the transmissive nonlinear slab are adopted here for semiconductors. These new sources are scalable both in THz energy and size. Furthermore, they can outperform the already demonstrated contact grating source in diffraction and THz generation efficiency. Compared to the lithium niobate sources, they are more feasible, thanks to the easier manufacturing and the longer pump wavelength. They can produce intense, nearly single-cycle THz pulses at higher frequencies. With 20 mJ pumping at 1.8 µm wavelength, 45 µJ THz energy, and 17 MV/cm focused peak electric field can be expected at 3 THz phase matching frequency from the transmissive nonlinear echelon slab setup consisting of a 4 mm thick structured plan-parallel gallium phosphide crystal.

Reversal of Photoinduced Bending of Crystals Due to Internal Refraction of Light

The well-known effect of bending of acicular crystals undergoing photochemical reactions is associated with the transformation gradient across the crystal thickness caused by the absorption of light. It is believed that the direction of bending is unambiguously dictated by the sign of the axial component of the reaction strain and due to the higher light intensity on the irradiated side of the crystal. In this study, it is shown experimentally and theoretically that thin crystals with a convex irradiated surface bend in the opposite direction if their thickness is less than the light penetration depth. The reversal of the bending direction is due to the lens effect, able to overcome the absorption of light in a thin crystal and provide a higher light intensity on the rear side of the crystal. A crystal of [Co(NO3)5NO2]Cl(NO3) experiencing nitro-nitrito photoisomerization, begins to bend in the opposite direction after it is thinned by etching to 2 µm when irradiated at the wavelengths of 523 nm, 465 nm, and 403 nm, absorbed at a depth of more than 10 µm in the crystal, but bends in the normal direction under 350 nm light absorbed at a depth of about 1 µm. The experimental results are fully confirmed by modeling the interaction of plane EM wave with crystals of various cross sections.

Investigating Microstructural Evolution and Its Influence on Tribological Behaviors of In-Situ Formed VCp Reinforced Iron-Based Composites with Variable Mn Content.

In this work, we fabricated VCp-reinforced iron-based composites (VCFCs) by adjusting the amount of Mn elements and investigated how the concentration of Mn affected the microstructural characteristics of Vanadium carbide (VC) and the texture of the iron matrix, and the influence of microstructure on tribological behaviors should be investigated. We demonstrated that VC changed from thick dendrite crystals (~50 μm) to tiny equiaxed crystals (~5 μm). Furthermore, the nucleation mechanism of VC also transformed from homogeneous nucleation to heterogeneous nucleation due to the lower Gibbs free energy of TiC and the tailoring effect of the Mn elements. In addition, γ-Fe in the FCC structure gradually increased and ascribed an increase of Mn content to the lower transformation temperature of martensite. Furtherly, particulate features and phase constitution could contribute to hardness and wear resistance. Higher hardness and excellent wear resistance occurred in the 3.0 Mn sample, which had a hardness of 869 HV and a wear rate of 1.77 × 10-6 mm3/(N·m). In addition, the adhesive wear could be the main wear mechanism in the 3.0 Mn sample, while the abrasive wear could be in the 4.5 Mn sample.

Terahertz Generation by Optical Rectification of 780 nm Laser Pulses in Pure and Sc-Doped ZnGeP2 Crystals

Terahertz wave generation through the optical rectification of 780 nm femtosecond laser pulses in ZnGeP2 crystals has been studied. All of the possible interactions of types I and II were analyzed by modeling and experimentally. We demonstrate the possibility of broadband “low-frequency” terahertz generation by an ee–e interaction (with two pumping waves and a generated terahertz wave; all of these had extraordinary polarization in the crystal) and “high-frequency” terahertz generation by an oe–e interaction. The arising possibility of achieving the narrowing of the terahertz generation bandwidth at the oe–e interaction using thicker ZnGeP2 crystals is experimentally confirmed. It has been found that the thermal annealing of as-grown ZnGeP2 crystals and their doping with a 0.01 mass % of Sc reduces the absorption in the “anomalous absorption” region (λ = 0.62–3 μm). The terahertz generation by the oo–e interaction in (110) ZnGeP2:Sc and the as-grown ZnGeP2 crystals of equal thicknesses was compared. It has been found that ZnGeP2:Sc is more efficient for 780 nm femtosecond laser pulses optical rectification.

Visible transparent mid-infrared broadband absorbers based on gradient refractive indexes and multi-size cavity resonances.

We proposed a multi-layered nanorod structure with the same tilt angle and different diameters, which has high visible transmittance and strong 3-5 µm absorption based on the principles of the gradient of the refractive index and the multi-size cavity resonances. The indium tin oxide (ITO) was selected as the target material to fabricate the structure by using a glancing angle deposition method. The experimental results show that when the deposition angle θ is 80°, swing deposition is successively done with the rotation angle φ of ±8°, ± 5°, ± 3°, and 0° on the surface of the substrate, and the quartz crystal microbalance thicknesses of ITO nanorods are 220 nm for each deposition, the average transmittance is 80.5% in the range of 400-800 nm and the integrated absorption is 86% in the 3-5 µm band. Such a simple, low-cost, and easy-to-fabricate device has potential applications in window stealth materials and other related fields.

Self-assembly assisted by microdroplet templates confinement for the preparation of ultramixed composite energetic particulates

Restricted by the macroscopic spatial scale conditions in traditional preparation methods, the improvement of delay precision of the delay composition gradually arrives at the bottleneck. Therefore, a microdroplet-confined coupling polymer self-assembly theory based on microfluidics was proposed to prepare ultramixed self-assembled composite energetic material particulates in order to make a breakthrough in its delay precision. Taking boron (B)/barium chromate (BaCrO4) delay composition as the research object, nano-BaCrO4 particles were prepared and microdroplet templates were generated by using the micromixing and microdispersing reaction systems respectively. With the excellent mixing efficiency of the micromixing reaction system, the effect of reactant concentration and temperature on crystal morphology and particle size of BaCrO4 was investigated, and the spectral response of BaCrO4 particles was analyzed on-line by using an on-line UV–vis spectrophotometer. The results indicated that the reactant concentration exerted a great influence on crystal morphology and particle size of BaCrO4, and the characteristic absorption peak of BaCrO4 was red-shifted regularly with the decrease of crystal thickness at low reactant concentration. Microdroplet templates for self-assembly of B/BaCrO4 nano-composite particles were generated by using a microdispersing reaction system, and the self-assembled B/BaCrO4 particulates were prepared. The particulates were characterized by thermal analysis and the delay precision was measured. The results exhibited that the composite energetic particulates with ultra-homogeneous mixing, excellent combustion performance and high delay precision were prepared. In summary, in this study, ultramixed self-assembled B/BaCrO4 particulates with high delay precision were prepared based on microfluidics, which can provide a novel technology and method for the preparation and mixing of other composites.

Highly Tunable Beyond-Room-Temperature Intrinsic Ferromagnetism in Cr-Doped Topological Crystalline Insulator SnTe Crystals.

The combination of topological phase and intrinsic beyond-room-temperature ferromagnetism is expected to realize the quantum anomalous Hall effect at a high temperature. However, no beyond-room-temperature intrinsic ferromagnetism has been reported in either topological insulator or topological crystalline insulator (TCI) so far. Here, we report Cr-doping in TCI-phase SnTe crystals which possess highly tunable beyond-room-temperature intrinsic ferromagnetism including Tc, magnetic moment, and coercivity by varying Cr contents and crystal thickness. With the increase of the Cr content, the Tc increases by 159 K from 221 to 380 K and the saturation magnetic moments increase by ∼23.6 times from 0.018 to 0.421 μB/f.u. This intrinsic beyond-room-temperature ferromagnetism is fully demonstrated by the anomalous Hall effect and magneto-optical Kerr effect in a single CrxSn1-xTe nanosheet. Moreover, the room-temperature tunneling magnetoresistance effect has been realized by using a CrxSn1-xTe flake, a Fe thin film, and a commercially compatible ultrathin AlOx tunneling barrier. This work indicates a great potential of CrxSn1-xTe crystals in room-temperature magnetoelectronic and spintronic devices.

Terahertz generation optimization in an OH1 nonlinear organic crystal pumped by a Cr:forsterite laser.

We present the results of experimental investigations of terahertz radiation generation conversion efficiency in an OH1 nonlinear organic crystal pumped by femtosecond laser pulses at 1240 nm wavelength. An influence of OH1 crystal thickness on the terahertz generation by optical rectification method was studied. It is shown that the optimal crystal thickness for the maximum conversion efficiency is 1 mm, which agrees with the previously made theoretical estimates.

Simulation of a cholesteric blue phase cell with large but finite thickness

We investigate the structure of a cholesteric blue phase (BP) liquid crystal cell of finite thickness under an electric field normal to the planar surfaces confining the liquid crystal. We carry out large scale simulations to consider cases in which the thickness of the BP liquid crystal is approximately 40 times the BP lattice constant (typical thickness in experiments), larger than that of previous simulation studies. Our calculations clearly demonstrate that the number of periodic structures along the thickness direction (thickness divided by the lattice constant) is discretized by the presence of confining surfaces. The stability of the so-called BP X structure over the BP I under the electric field, as well as the electrostriction, is confirmed. The metastability of the BP X structure after the cessation of the electric field, demonstrated in a recent experiment [Nat. Mater. 19, 94 (2020)] is also shown. We also perform calculations for the reflection spectra of the BP structures, and clearly observe the shift of the reflection peak due to electrostriction. Our study demonstrates the role of finite thickness on the behavior of a BP cell.

Thickness-Based Dispersion in Opal Photonic Crystals

Photonic crystals (PhCs) are types of colloidal crystals which demonstrate a host of exciting optical phenomena, the nature of which can lend insight into their structure and enable a range of potential applications in fields such as optics and optoelectronics,1 energy storage,2-6 and sensors for environmental monitoring, biomedicine and food preservation.7 Artificial opals8 are PhCs which can be formed easily using low-cost self-assembly methods and their structures are composed of highly ordered, close-packed, polymeric sphere arrays. While the optical behaviour of opals has received significant attention over the last number of decades, there is limited information on the effect of crystal thickness on the optical properties they display. Most studies focus their attention on the lattice parameters and refractive index contrast within the materials.9,10 Here, the relationship between volume fraction and crystal thickness using an evaporation-induced self-assembly (EISA) method of formation is established.11-13 The extent to which thickness can be used to manipulate the optical properties of the crystals is explored, focusing on the change in the photonic band gap (PBG). Specifically, the thickness-induced changes in the properties which define the PBG for a range of volume fractions. Through meticulous structural and optical characterization, primarily in the form of scanning electron microscopy (SEM) images and angle-resolved ultraviolet-visible (UV-Vis) spectroscopy, the quality of the crystals formed is examined, with thicknesses exceeding 40 layers grown from volume fractions below 0.15 %, for the first time, to our knowledge. Crystal structure is correlated to optical fingerprint, shown in the form of transmission spectra in the UV-Vis region.We expect this work to provide our colleagues in the scientific community with a direct correlation between crystal thickness and the optical fingerprint of opal PhCs. Our analysis also stands as a manual to aid any future attempts at the growth of ultra-thick colloidal crystals. Such research may act as a precursor to further developments in materials employed in the photonics, sensing, energy storage and related communities. References 1 M. I. Shalaev, W. Walasik, A. Tsukernik, Y. Xu, and N. M. Litchinitser, Nature Nanotechnology 14, 31 (2019). 2 D. McNulty, A. Lonergan, S. O'Hanlon, and C. O'Dwyer, Solid State Ionics 314, 195 (2018). 3 D. McNulty, H. Geaney, D. Buckley, and C. O'Dwyer, Nano Energy 43, 11 (2018). 4 D. McNulty, E. Carroll, and C. O'Dwyer, Advanced Energy Materials 7, 1602291 (2017). 5 E. Armstrong, D. McNulty, H. Geaney, and C. O’Dwyer, ACS Applied Materials & Interfaces 7, 27006 (2015). 6 D. McNulty, H. Geaney, Q. Ramasse, and C. O'Dwyer, Adv. Funct. Mater. 30, 2005073 (2020). 7 J. Hou, M. Li, and Y. Song, Nano Today 22, 132 (2018). 8 E. Armstrong and C. O'Dwyer, Journal of Materials Chemistry C 3, 6109 (2015). 9 D. R. Solli and J. M. Hickmann, Optical Materials 33, 523 (2011). 10 S. G. Romanov, Physics of the Solid State 59, 1356 (2017). 11 Q. Jiang, C. Li, S. Shi, D. Zhao, L. Xiong, H. Wei, and L. Yi, Journal of Non-Crystalline Solids 358, 1611 (2012). 12 J. Zhang, Y. Li, X. Zhang, and B. Yang, Advanced Materials 22, 4249 (2010). 13 A. Lonergan, C. Hu, and C. O'Dwyer, Phys. Rev. Materials 4, 065201 (2020). 14 S. O'Hanon, D. McNulty, R. Tian, J. Coleman, and C. O'Dwyer, J. Electrochem. Soc. 167, 140532 (2020). Figure 1. Optical and structural analysis for 350 nm PS opals formed by EISA. Analysis presented in the form of transmission spectra obtained for samples formed from a range of five volume fractions, labelled by their dilution factors (a,d,g), sample plan view SEM images (b,e,f), and sample cross-sectional SEM images (c,f,i). (a-c) correspond to regions of maximum opal thickness, (d-f) to regions of lesser thickness, (g-i) to regions of minimal thickness. Figure 1

(Invited, Digital Presentation) Vertical Heterogeneous Integration of Metal Halide Perovskite Quantum-Wires/Nanowires for Flexible Narrowband Photodetectors

Charge collection narrowing (CCN) has been reported to be an efficient strategy to achieve optical filter-free narrowband photodetection (NPD) with metal halide perovskite (MHP) single crystals. However, the necessity of utilizing thick crystals in CCN limits their applications in large scale, flexible, self-driven, and high-performance optoelectronics. Here, for the first time, we fabricate vertically integrated MHP quantum wire/nanowire (QW/NW) array-based photodetectors in nanoengineered porous alumina membranes (PAMs) showing self-driven broadband photodetection (BPD) and NPD capability simultaneously. Two cutoff detection edges of the NPDs are located at around 770 and 730 nm, with a full-width at half-maxima (fwhm) of around 40 nm. The optical bandgap difference between the NWs and the QWs, in conjunction with the high carrier recombination rate in QWs, contributes to the intriguing NPD performance. Thanks to the excellent mechanical flexibility of the PAMs, a flexible NPD is demonstrated with respectable performance. Our work here opens a new pathway to design and engineer a nanostructured MHP for novel color selective and full color sensing devices. Figure 1