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Layered {\alpha}-RuCl3 is a promising material to potentially realize the long-sought Kitaev quantum spin liquid with fractionalized excitations. While evidence of this exotic state has been reported under a modest in-plane magnetic field, such behavior is largely inconsistent with theoretical expectations of Kitaev phases emerging only in out-of-plane fields. These predicted field-induced states have been mostly out of reach due to the strong easy-plane anisotropy of bulk crystals, however. We use a combination of tunneling spectroscopy, magnetotransport, electron diffraction, and ab initio calculations to study the layer-dependent magnons, anisotropy, structure, and exchange coupling in atomically thin samples. Due to structural distortions, the sign of the average off-diagonal exchange changes in monolayer {\alpha}-RuCl3, leading to a reversal of magnetic anisotropy to easy-axis. Our work provides a new avenue to tune the magnetic interactions in {\alpha}-RuCl3 and allows theoretically predicted quantum spin liquid phases for out-of-plane fields to be more experimentally accessible.

Carbon-based nanomaterials mainly including carbon nanotubes (CNTs), graphene, and graphene oxide (GO) have superior properties of low density, outstanding strength, and high hardness. Compared with ceramic reinforcements, small amount of carbon-based nanomaterials can significantly improve the mechanical properties of metal matrix composites (MMCs) and ceramic matrix composites (CMCs). However, CNTs and graphite always aggregate or degrade during the fabrication with a high temperature, especially in MMCs. GO has the advantages of easier to be dispersed in other materials and better high-temperature stability. Laser-directed energy deposition (DED) has been used to fabricate GO-MMCs and GO-CMCs due to the unique capabilities of coating, remanufacturing, and producing functionally graded materials. Laser DED, as a fusion manufacturing process, could fully melt the material powders, which could refine the microstructure and increase the density and mechanical properties. However, GO could react with matrix materials at high temperatures. The survival, degradation, and reactions of GO in laser DED fabricated GO-MMCs and GO-CMCs are still unknown. There is also no investigation on the reinforcement mechanisms of GO in metal matrix materials and ceramic matrix materials in the laser DED process. In this study, GO-reinforced Ti (GO-Ti) and GO-reinforced zirconia toughened alumina (GO-ZTA) parts were fabricated by laser DED process. Raman spectrum, XRD analysis, and EDS analysis have been applied to investigate the forms of GO in both DED fabricated GO-MMCs and GO-CMCs. The reinforcement mechanisms of GO on microhardness and compressive properties of MMCs and CMCs have been analyzed.

The nature of point defects in hexagonal boron nitride (hBN) is of current interest for the potential to alter its optical and electrical properties. The strong interaction between neutrons and the...

Moiré magnetism, parallel with moiré electronics that has led to novel correlated and topological electronic states, emerges as a new venue to design and control exotic magnetic phases in twisted magnetic two-dimensional (2D) crystals. Noncollinear spin texture emerging from twisted 2D magnets with collinear spins is the most profound consequence of moiré magnetism and forms the basis for realizing novel magnetic orders and excitations. Yet, no direct experimental observation of noncollinear spins in moiré magnets have been made despite recent theoretical and experimental efforts. Here, we report the evidence of noncollinear spin texture in 2D twisted double bilayer (tDB) magnet chromium triiodide (CrI3). By studying the magnetic field dependent magnetic circular dichroism (MCD) in tDB CrI3, we distinguished the noncollinear spins with a gradual spin flop process from the collinear spins with sudden spin flip transitions, and identified a net magnetization emerging from the collinear spins. By examining the twist angle dependence, we demonstrated that both noncollinear spins and net magnetization are present at twist angles from 0.5^o to 5^o, but are most prominent in the 1.1^o tDB CrI3. By tracking the temperature dependent MCD of the 1.1^o tDB CrI3, we further resolved a new critical temperature of 22 K, for the onset of the net magnetization and the softening of the noncollinear spins, which is dramatically suppressed from the Néel temperature of 45 K for natural few layers. Our results establish the emergence of noncollinear spins from magnetic moiré superlattices and provide a versatile platform to explore nontrivial magnetism with noncollinear spins.

Hexagonal boron nitride (hBN) is an important insulator that is incorporated into numerous 2D electronic, optoelectronic, and photonic devices, whereas natural hBN is a mixture of 20% 10B and 80% 11B isotopes, and monoisotopic hBN is a variant with just a single boron isotope, either 10B or 11B. Consequently, monoisotopic hBN has a higher thermal conductivity and a stronger neutron absorption (in the case of h10BN), making it superior for neutron detectors, heat management materials in nano flexible electronic devices, and phonon polariton-based nanophotonics. Here we synthesized approximately monoisotopic hBN using boron powder containing a single boron isotope and nitrogen, and grew single crystals from a Fe–Cr metal flux at atmospheric pressure. Narrow Raman peaks from the shear (≤1.3 cm−1) and intralayer (≤3.3 cm−1) modes demonstrate that the crystals are highly ordered. In the photoluminescence spectra, the presence of phonon-assistant transition peaks is also indicative of the high-quality of the crystals. This growth protocol permits us to get rid of the emission at 4.1 eV. This work provides a novel material for studying the fundamental properties of isotopic effects and the high-performance hBN device.

Carbon-based nanomaterials mainly including carbon nanotubes (CNTs), graphene, and graphene oxide (GO) have superior properties of low density, outstanding strength, and high hardness. Compared with ceramic reinforcements, a small amount of carbon-based nanomaterials can significantly improve the mechanical properties of metal matrix composites (MMCs) and ceramic matrix composites (CMCs). However, CNTs and graphite always aggregate or degrade during the fabrication with a high temperature, especially in MMCs. GO has the advantages of easier to be dispersed in other materials and better high-temperature stability. Laser directed energy deposition (DED), has been used to fabricate GO-MMCs and GO-CMCs due to the unique capabilities of coating, remanufacturing, and producing functionally graded materials. Laser DED, as a fusion manufacturing process, could fully melt the material powders, which could refine the microstructure and increase the density and mechanical properties. However, GO could react with matrix materials at high temperatures. The survival, degradation, and reactions of GO in laser DED fabricated GO-MMCs and GO-CMCs are still unknown. There is also no investigation on the reinforcement mechanisms of GO in metal matrix materials and ceramic matrix materials in the laser DED process. In this study, GO reinforced Ti (GO-Ti) and GO reinforced zirconia toughened alumina (GO-ZTA) parts were fabricated by laser DED process. Raman spectrum, XRD analysis, and EDS analysis have been applied to investigate the forms of GO in both DED fabricated GO-MMCs and GO-CMCs. The reinforcement mechanisms of GO on microhardness and compressive properties of MMCs and CMCs have been analyzed.

Using polarization-resolved Raman spectroscopy, we investigate layer number, temperature, and magnetic field dependence of Raman spectra in one- to four-layer $\mathrm{CrI_{3}}$. Layer-number-dependent Raman spectra show that in the paramagnetic phase a doubly degenerated $E_{g}$ mode of monolayer $\mathrm{CrI_{3}}$ splits into one $A_{g}$ and one $B_{g}$ mode in N-layer (N > 1) $\mathrm{CrI_{3}}$ due to the monoclinic stacking. Their energy separation increases in thicker samples until an eventual saturation. Temperature-dependent measurements further show that the split modes tend to merge upon cooling but remain separated until 10 K, indicating a failed attempt of the monoclinic-to-rhombohedral structural phase transition that is present in the bulk crystal. Magnetic-field-dependent measurements reveal an additional monoclinic distortion across the magnetic-field-induced layered antiferromagnetism-to-ferromagnetism phase transition. We propose a structural change that consists of both a lateral sliding toward the rhombohedral stacking and a decrease in the interlayer distance to explain our experimental observations., The article was published in ACS Nano on June 2

Using polarization-resolved Raman spectroscopy, we investigate layer number, temperature, and magnetic field dependence of Raman spectra in one- to four-layer CrI

The highest quality hexagonal boron nitride (hBN) crystals are grown from molten solutions. For hBN crystal growth at atmospheric pressure, typically the solvent is a combination of two metals, one with a high boron solubility and the other to promote nitrogen solubility. In this study, we demonstrate that high-quality hBN crystals can be grown at atmospheric pressure using pure iron as a flux. The ability to produce excellent-quality hBN crystals using pure iron as a solvent is unexpected, given its low solubility for nitrogen. The properties of crystals produced with this flux matched the best values ever reported for hBN: a narrow Raman E2g vibration peak (7.6 cm–1) and strong phonon-assisted peaks in the photoluminescence spectra. To further test their quality, the hBN crytals were used as a substrate for WSe2 epitaxy. WSe2 was deposited with a low nucleation density, indicating the low defect density of the hBN. Lastly, the carrier tunneling through our hBN thin layers (3.5 nm) follows the Fowler–Nordheim model, with a barrier height of 3.7 eV, demonstrating hBN’s superior electrical insulating properties. This ability to produce high-quality hBN crystals in such a simple, environmentally friendly and economical process will advance two-dimensional material research by enabling integrated devices.

Twist engineering, or the alignment of two-dimensional (2D) crystalline layers with desired orientations, has led to tremendous success in modulating the charge degree of freedom in hetero- and homo-structures, in particular, in achieving novel correlated and topological electronic phases in moiré electronic crystals. However, although pioneering theoretical efforts have predicted nontrivial magnetism and magnons out of twisting 2D magnets, experimental realization of twist engineering spin degree of freedom remains elusive. Here, we leverage the archetypal 2D Ising magnet chromium triiodide (CrI3) to fabricate twisted double bilayer homostructures with tunable twist angles and demonstrate the successful twist engineering of 2D magnetism in them. Using linear and circular polarization-resolved Raman spectroscopy, we identify magneto-Raman signatures of a new magnetic ground state that is sharply distinct from those in natural bilayer (2L) and four-layer (4L) CrI3. With careful magnetic field and twist angle dependence, we reveal that, for a very small twist angle (~ 0.5 degree), this emergent magnetism can be well-approximated by a weighted linear superposition of those of 2L and 4L CI3 whereas, for a relatively large twist angle (~ 5 degree), it mostly resembles that of isolated 2L CrI3. Remarkably, at an intermediate twist angle (~ 1.1 degree), its magnetism cannot be simply inferred from the 2L and 4L cases, because it lacks sharp spin-flip transitions that are present in 2L and 4L CrI3 and features a dramatic Raman circular dichroism that is absent in natural 2L and 4L ones. Our results demonstrate the possibility of designing and controlling the spin degree of freedom in 2D magnets using twist engineering.

Significance The two-dimensional (2D) magnetic semiconductor CrI3 hosts a variety of strong and tunable magneto-optical effects and allows for the development of novel magneto-optical devices. While the elastic magneto-optical effects in CrI3 are well understood, its recently discovered inelastic magneto-Raman effect remains to have case-specific interpretations varying upon the thickness of CrI3. We perform comprehensive Raman measurements on 2D CrI3 with polarization, temperature, layer number, and magnetic field dependence. We resolve a Davydov-split–induced N-fold multiplet in N-layer CrI3 and reveal the distinct magneto-Raman behaviors of individual phonons within the multiplet. Our results discover a layered-magnetism–coupled phonon scattering mechanism that explains the rich magneto-Raman effect in CrI3 of arbitrary thickness and elucidates the spin–phonon coupling physics in layered magnets., We used a combination of polarized Raman spectroscopy experiment and model magnetism–phonon coupling calculations to study the rich magneto-Raman effect in the two-dimensional (2D) magnet CrI3. We reveal a layered-magnetism–assisted phonon scattering mechanism below the magnetic onset temperature, whose Raman excitation breaks time-reversal symmetry, has an antisymmetric Raman tensor, and follows the magnetic phase transitions across critical magnetic fields, on top of the presence of the conventional phonon scattering with symmetric Raman tensors in N-layer CrI3. We resolve in data and by calculations that the first-order Ag phonon of the monolayer splits into an N-fold multiplet in N-layer CrI3 due to the interlayer coupling (N≥2) and that the phonons within the multiplet show distinct magnetic field dependence because of their different layered-magnetism–phonon coupling. We further find that such a layered-magnetism–phonon coupled Raman scattering mechanism extends beyond first-order to higher-order multiphonon scattering processes. Our results on the magneto-Raman effect of the first-order phonons in the multiplet and the higher-order multiphonons in N-layer CrI3 demonstrate the rich and strong behavior of emergent magneto-optical effects in 2D magnets and underline the unique opportunities of spin–phonon physics in van der Waals layered magnets.

International audience; Hexagonal boron nitride (hBN) is attracting much attention due to its tremendous applications including nanophotonic and electronic devices, substrates for two-dimensional (2D) materials, heat management materials, etc. To achieve the best device performance, large area hBN single crystals are required. Herein, large area (>500 microns each) high-quality (defect density < 0.52/μm2) bulk hBN single crystals are grown from molten metal solutions with a temperature gradient. The narrow Raman linewidths of the intralayer E2g mode peak and the interlayer shear mode, the strong and sharp phonon-assisted transition photoluminescence peaks, and the high thermal conductivity demonstrate that the hBN produced by this method are high crystal quality with a low density of defects. Atomic force microscope images show that atomically flat layers of hBN can be produced by exfoliation. This study not only demonstrates a new strategy for growing large hBN single crystals, but also provides high quality thick and thin hBN layers for nano device applications

Exploring new parameter regimes to realize and control novel phases of matter has been a main theme in modern condensed matter physics research. The recent discovery of two-dimensional (2D) magnetism in nearly freestanding monolayer atomic crystals has already led to observations of a number of novel magnetic phenomena absent in bulk counterparts. Such intricate interplays between magnetism and crystalline structures provide ample opportunities for exploring quantum phase transitions in this new 2D parameter regime. Here, using magnetic field- and temperature-dependent circularly polarized Raman spectroscopy of phonons and magnons, we map out the phase diagram of chromium triiodide (CrI_{3}) that has been known to be a layered antiferromagnet (AFM) in its 2D films and a ferromagnet (FM) in its three-dimensional (3D) bulk. However, we reveal a novel mixed state of layered AFM and FM in 3D CrI_{3} bulk crystals where the layered AFM survives in the surface layers, and the FM appears in deeper bulk layers. We then show that the surface-layered AFM transits into the FM at a critical magnetic field of 2 T, similar to what was found in the few-layer case. Interestingly, concurrent with this magnetic phase transition, we discover a first-order structural phase transition that alters the crystallographic point group from C_{3i} (rhombohedral) to C_{2h} (monoclinic). Our result not only unveils the complex single-magnon behavior in 3D CrI_{3}, but it also settles the puzzle of how CrI_{3} transits from a bulk FM to a thin-layered AFM semiconductor, despite recent efforts in understanding the origin of layered AFM in CrI_{3} thin layers, and reveals the intimate relationship between the layered AFM-to-FM and the crystalline rhombohedral-to-monoclinic phase transitions. These findings further open opportunities for future 2D magnet-based magnetomechanical devices.

We use a combination of polarized Raman spectroscopy experiment and model magnetism-phonon coupling calculations to study the rich magneto-Raman effect in the two-dimensional (2D) magnet $\mathrm{CrI_3}$. We reveal a novel layered-magnetism-assisted phonon scattering mechanism below the magnetic onset temperature, whose Raman excitation breaks time-reversal symmetry, has an antisymmetric Raman tensor, and follows the magnetic phase transitions across critical magnetic fields, on top of the presence of the conventional phonon scattering with symmetric Raman tensors in $N$-layer $\mathrm{CrI_3}$. We resolve in data and by calculations that the 1st-order $A_g$ phonon of monolayer splits into a $N$-fold multiplet in $N$-layer $\mathrm{CrI_3}$ due to the interlayer coupling ($N$>=2) and that the phonons with the multiple show distinct magnetic field dependence because of their different layered-magnetism-phonon coupling. We further find that such a layered-magnetism-phonon coupled Raman scattering mechanism extends beyond 1st-order to higher-order multi-phonon scattering processes. Our results on magneto-Raman effect of the 1st-order phonons in the multiplet and the higher-order multi-phonons in $N$-layer $\mathrm{CrI_3}$ demonstrate the rich and strong behavior of emergent magneto-optical effects in 2D magnets and underlines the unique opportunities of new spin-phonon physics in van der Waals layered magnets., 16 pages, 4 figures + supplementary material

Layered transition metal oxides remain a relatively unexplored front in the study of two-dimensional (2D) van der Waals materials, providing opportunities to further advance semiconductor physics a...

V2O5 with a layered van der Waals (vdW) structure has been widely studied because of the material's potential in applications such as battery electrodes. In this work, microelectronic devices were fabricated to study the electrical and optical properties of mechanically exfoliated multilayered V2O5 flakes. Raman spectroscopy was used to determine the crystal structure axes of the nanoflakes and revealed that the intensities of the Raman modes depend strongly on the relative orientation between the crystal axes and the polarization directions of incident/scattered light. Angular dependence of four-probe resistance measured in the van der Pauw (vdP) configuration revealed an in-plane anisotropic resistance ratio of ∼100 between the a and b crystal axes, the largest in-plane transport anisotropy effect experimentally reported for two-dimensional (2D) materials to date. This very large resistance anisotropic ratio is explained by the nonuniform current flow in the vdP measurement and an intrinsic mobility anisotropy ratio of 10 between the a and b crystal axes. Room-temperature electron Hall mobility up to 7 cm2/(V s) along the high-mobility direction was obtained. This work demonstrates V2O5 as a layered 2D vdW oxide material with strongly anisotropic optical and electronic properties for novel applications.

We have investigated the interlayer shear and breathing phonon modes in MoS$_{2}$ with pure 3R and 2H stacking order by using polarization-dependent ultralow-frequency Raman spectroscopy. We observe up to three shear branches and four breathing branches in MoS$_{2}$ with thickness from 2 to 13 layers. The breathing modes show the same Raman activity behavior for both polytypes, but the 2H breathing frequencies are consistently several wavenumbers higher than the 3R breathing frequencies, signifying that 2H MoS$_{2}$ has slightly stronger interlayer lattice coupling than 3R MoS$_{2}$. In contrast, the shear-mode Raman spectra are strikingly different for 2H and 3R MoS$_{2}$. While the strongest shear mode corresponds to the highest-frequency branch in the 2H structure, it corresponds to the lowest-frequency branch in the 3R structure. Such distinct and complementary Raman spectra of the 3R and 2H polytypes allow us to survey a broad range of shear modes in MoS$_{2}$, from the highest to lowest branch. By combining the linear chain model, group theory, effective bond polarizability model and first-principles calculations, we can account for all the major observations in our experiment., 18 pages, 8 figures (supplemental material: 23 pages, 13 figures). 2D Materials, Accepted Manuscript online 24 January 2019

We use a combination of Raman spectroscopy and transport measurements to study thin flakes of the type-II Weyl semimetal candidate $\mathrm{MoT}{\mathrm{e}}_{2}$ protected from oxidation. In contrast to bulk crystals, which undergo a phase transition from monoclinic to the inversion symmetry breaking, orthorhombic phase below $\ensuremath{\sim}250\phantom{\rule{0.16em}{0ex}}\mathrm{K}$, we find that in moderately thin samples below $\ensuremath{\sim}12\phantom{\rule{0.16em}{0ex}}\mathrm{nm}$, a single orthorhombic phase exists up to and beyond room temperature. This could be due to the effect of $c$-axis confinement, which lowers the energy of an out-of-plane hole band and stabilizes the orthorhombic structure. Our results suggest that Weyl nodes, predicated upon inversion symmetry breaking, may be observed in thin $\mathrm{MoT}{\mathrm{e}}_{2}$ at room temperature.

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We employ low-frequency Raman spectroscopy to study the nearly commensurate (NC) to commensurate (C) charge density wave (CDW) transition in 1T-TaS2 ultrathin flakes protected from oxidation. We identify new modes originating from C phase CDW phonons that are distinct from those seen in bulk 1T-TaS2. We attribute these to CDW modes from the surface layers. By monitoring individual modes with temperature, we find that surfaces undergo a separate, low-hysteresis NC-C phase transition that is decoupled from the transition in the bulk layers. This indicates the activation of a secondary phase nucleation process in the limit of weak interlayer interaction, which can be understood from energy considerations.

Atomically thin NbSe2 is a metallic layered transition metal dichalcogenide with novel charge-density-wave (CDW) and superconductive phases. Properties of NbSe2 atomic layers are sensitive to interlayer coupling. Here we investigate the interlayer phonons of few-layer NbSe2 by ultralow-frequency Raman spectroscopy. We observe both the interlayer breathing modes and shear modes at frequencies below 40 cm−1 for samples of 2–15 layers. Their frequency, Raman activity, and environmental instability depend systematically on the layer number. We account for these results by a combination of linear-chain model, group theory and first-principles calculations. We find that, although NbSe2 has different stacking order from MoS2, MoSe2, WS2 and WSe2, they share the same crystal symmetry groups and exhibit similar Raman selection rules for interlayer phonons. In addition, the interlayer phonon modes evolve smoothly from T = 300 to 8 K, with no observable response to the CDW formation in NbSe2. This finding indicates that the atomic registry between adjacent NbSe2 layers is well preserved in the CDW transition.

We investigate the ultralow-frequency Raman response of atomically thin ReS2, a special type of two-dimensional (2D) semiconductors with unique distorted 1T structure. Bilayer and few-layer ReS2 exhibit rich Raman spectra at frequencies below 50 cm-1, where a panoply of interlayer shear and breathing modes are observed. The emergence of these interlayer phonon modes indicate that the ReS2 layers are coupled and stacked orderly, in contrast to the general belief that the ReS2 layers are decoupled from one another. While the interlayer breathing modes can be described by a linear chain model as in other 2D layered crystals, the shear modes exhibit distinctive behavior due to the in-plane lattice distortion. In particular, the two shear modes in bilayer ReS2 are non-degenerate and well separated in the Raman spectrum, in contrast to the doubly degenerate shear modes in other 2D materials. By carrying out comprehensive first-principles calculations, we can account for the frequency and Raman intensity of the interlayer modes, and determine the stacking order in bilayer ReS2.