Bilayer Crystals Research Articles

Direct observation of mono-layer, bi-layer, and tri-layer charge density waves in 1T-TaS2 by transmission electron microscopy without a substrate

Charge-density-waves, which occur mainly in low-dimensional systems, have a macroscopic wave function similar to superfluids and superconductors. Kosterlitz–Thouless transition is observed in superfluids and superconductors, but the presence of Kosterlitz–Thouless transition in ultra-thin charge-density-waves systems has been an open problem. We report the direct real-space observation of charge-density-waves with new order states in mono-layer, bi-layer, and tri-layer 1T-TaS2 crystals using a low voltage scanning-transmission-electron-microscopy without a substrate. This method is ideal to observe local atomic structures and possible defects. We clearly observed that the mono-layer crystal has a new triclinic stripe charge-density-waves order without satisfying the triple q condition q1 + q2 + q3 = 0. A strong electron-phonon interaction gives rise to new crevasse (line) type defects instead of disclination (point) type defects due to the Kosterlitz–Thouless transition. These results reaffirm the importance of the electron-phonon interaction in mono-layer nanophysics.

Thermally induced bilayered crystals in a solution-processed polycrystalline thin film of phenylterthiophene-based monoalkyl smectic liquid crystals and their effect on FET mobility

Herein, a series of asymmetric monoalkyl terthiophene derivatives, Ph-(Tp)3-Cn, (6 ≤ n ≤ 18), were synthesized to study the phase transition from monolayered crystal to bilayered crystal, leading to a significant increase of OFET mobility.

Facile construction of dual bandgap optical encoding materials with PS@P(HEMA-co-AA)/SiO2-TMPTA colloidal photonic crystals

An operable strategy for the construction of dual-reflex optical code materials from bilayer or Janus-structure colloidal photonic crystals (CPCs) has been established in this work. In this process, monodispersed submicrometer polystryene@poly(2-hydroxyethyl methacrylate-co-acrylic acid) hydrogel microspheres with soft-shell/hard-core structure and monodispersed colloidal silica spheres were fabricated. These two kinds of colloidal units can be facilely integrated into a single material without optical signal interference because they are well isolated for the immiscibility between water and ethoxylated trimethylolpropane triacrylate (TMPTA) and the upper layer of SiO2-TMPTA is a kind of transparent. Moreover, diverse optical code series with different dual photonic bandgaps can be obtained via tuning the colloid sizes. Compared to the conventional single-reflex CPCs, the as-prepared dual-reflex optical code materials represented high information capacity in encoding process. More interesting, delicate code pattern has been also achieved on the optical film via the silk-screen printing technique, which will greatly extend the dual-reflex optical code materials to practical uses in areas containing bio-encoding, anti-counterfeiting, and flexible displays.

GaN: From three- to two-dimensional single-layer crystal and its multilayer van der Waals solids

Three-dimensional (3D) GaN is a III-V compound semiconductor with potential optoelectronic applications. In this paper, starting from 3D GaN in wurtzite and zinc-blende structures, we investigated the mechanical, electronic, and optical properties of the 2D single-layer honeycomb structure of GaN ($g\ensuremath{-}\mathrm{GaN}$) and its bilayer, trilayer, and multilayer van der Waals solids using density-functional theory. Based on high-temperature ab initio molecular-dynamics calculations, we first showed that $g\ensuremath{-}\mathrm{GaN}$ can remain stable at high temperature. Then we performed a comparative study to reveal how the physical properties vary with dimensionality. While 3D GaN is a direct-band-gap semiconductor, $g\ensuremath{-}\mathrm{GaN}$ in two dimensions has a relatively wider indirect band gap. Moreover, 2D $g\ensuremath{-}\mathrm{GaN}$ displays a higher Poisson ratio and slightly less charge transfer from cation to anion. In two dimensions, the optical-absorption spectra of 3D crystalline phases are modified dramatically, and their absorption onset energy is blueshifted. We also showed that the physical properties predicted for freestanding $g\ensuremath{-}\mathrm{GaN}$ are preserved when $g\ensuremath{-}\mathrm{GaN}$ is grown on metallic as well as semiconducting substrates. In particular, 3D layered blue phosphorus, being nearly lattice-matched to $g\ensuremath{-}\mathrm{GaN}$, is found to be an excellent substrate for growing $g\ensuremath{-}\mathrm{GaN}$. Bilayer, trilayer, and van der Waals crystals can be constructed by a special stacking sequence of $g\ensuremath{-}\mathrm{GaN}$, and they can display electronic and optical properties that can be controlled by the number of $g\ensuremath{-}\mathrm{GaN}$ layers. In particular, their fundamental band gap decreases and changes from indirect to direct with an increasing number of $g\ensuremath{-}\mathrm{GaN}$ layers.

Charge-Induced Second-Harmonic Generation in Bilayer WSe2.

Controlling nonlinear light-matter interaction is important from a fundamental science point of view as well as a basis for future optoelectronic devices. Recent advances in two-dimensional crystals have created opportunities to manipulate nonlinear processes electrically. Here we report a strong second-harmonic generation (SHG) in a 2D WSe2 bilayer crystal caused by a back gate field. This unusual process takes place only when the gate polarity causes charge accumulation rather than depletion. Analysis based on a bond-charge model traces the origin of SHG to the nonuniform field distribution within a single monolayer, caused by the accumulated submonolayer screening charge in the tungsten plane. We name this phenomenon charge-induced SHG (CHISHG), which is fundamentally different from the field- or current-induced SHG. Our findings provide a potentially valuable technique for understanding and noninvasive probing of charge and current distributions in future low dimensional electronic devices.

Moiré Nanosphere Lithography

We have developed moiré nanosphere lithography (M-NSL), which incorporates in-plane rotation between neighboring monolayers, to extend the patterning capability of conventional nanosphere lithography (NSL). NSL, which uses self-assembled layers of monodisperse micro/nanospheres as masks, is a low-cost, scalable nanofabrication technique and has been widely employed to fabricate various nanoparticle arrays. Combination with dry etching and/or angled deposition has greatly enriched the family of nanoparticles NSL can yield. In this work, we introduce a variant of this technique, which uses sequential stacking of polystyrene nanosphere monolayers to form a bilayer crystal instead of conventional spontaneous self-assembly. Sequential stacking leads to the formation of moiré patterns other than the usually observed thermodynamically stable configurations. Subsequent O2 plasma etching results in a variety of complex nanostructures. Using the etched moiré patterns as masks, we have fabricated complementary gold nanostructures and studied their optical properties. We believe this facile technique provides a strategy to fabricate complex nanostructures or metasurfaces.

Revealing the Preferred Interlayer Orientations and Stackings of Two‐Dimensional Bilayer Gallium Selenide Crystals

Characterizing and controlling the interlayer orientations and stacking orders of two-dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor-phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA' and AB stacking) in as-grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga-terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals.

Revealing the Preferred Interlayer Orientations and Stackings of Two‐Dimensional Bilayer Gallium Selenide Crystals

AbstractCharacterizing and controlling the interlayer orientations and stacking orders of two‐dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor‐phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA′ and AB stacking) in as‐grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga‐terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals.

Synthesis of graphene crystals from solid waste plastic by chemical vapor deposition

Here, we report the synthesis of high quality single crystal graphene on polycrystalline Cu foil using solid waste plastic as carbon source in an ambient pressure (AP) chemical vapor deposition (CVD) process. Gas chromatography analysis shows that the waste plastic is rich in polyethylene and polystyrene based polymer components. The growth of individual crystal strongly influenced by the injection rate of decomposed polymeric components generated during pyrolysis of waste plastic. Synthesis of large hexagonal and round shape single crystal graphene are achieved with a controlled rate of pyrolysis for the waste plastic. Raman studies confirm high quality of the graphene crystals independent of hexagonal and round shapes. Again, nucleation of bilayer or few-layer graphene crystals are observed with a higher injection rate of decomposed polymeric components. The evolution of hexagonal graphene crystals synthesized by AP-CVD process from waste plastic can be significant to obtain large single crystal graphene and stacked bi-layer structure. Our findings shows that solid waste plastic can be directly use as a feedstock for high quality graphene growth and thereby converting to a significantly value added product.

A computational investigation of the phase behavior and capillary sublimation of water confined between nanoscale hydrophobic plates

Thin films of water under nanoscopic confinement are prevalent in natural and manufactured materials. To investigate the equilibrium and dynamic behavior of water in such environments, we perform molecular dynamics simulations of water confined between atomistically detailed hydrophobic plates at T = 298 K for pressures (-0.1) ≤ P ≤ 1.0 GPa and plate separations of 0.40 ≤ d ≤ 0.80 nm. From these simulations, we construct an expanded P-d phase diagram for confined water, and identify and characterize a previously unreported confined monolayer ice morphology. We also study the decompression-induced sublimation of bilayer ice in a d = 0.6 nm slit, employing principal component analysis to synthesize low-dimensional embeddings of the drying trajectories and develop insight into the sublimation mechanism. Drying is observed to proceed by the nucleation of a bridging vapor cavity at one corner of the crystalline slab, followed by expansion of the cavity along two edges of the plates, and the subsequent recession of the remaining promontory of bilayer crystal into the bulk fluid. Our findings have implications for the understanding of diverse phenomena in materials science, nanofluidics, and protein folding and aggregation.

Optical manifestations of symmetry breaking in bilayer graphene

We propose a spectroscopic method of identifying broken symmetry states of bilayer graphene. We demonstrate theoretically that, in contrast to gapped states, a strained bilayer crystal or nematic phase of the electronic liquid are distinguishable by the dependence of the lineshape of absorption on the polarization of the light. This property is characteristic for both the infrared and far-infrared spectral ranges, which correspond to the absorption by transitions between low-energy bands and split bands, and transitions between the low-energy valence and conduction bands, respectively.

Spontaneous Formation of Two-Dimensional and Three-Dimensional Cholesterol Crystals in Single Hydrated Lipid Bilayers

Grazing incidence x-ray diffraction measurements were performed on single hydrated bilayers and monolayers of Ceramide/Cholesterol/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocyholine at varying concentrations. There are substantial differences in the phase and structure behavior of the crystalline domains formed within the bilayers relative to the corresponding monolayers, due to interactions between the opposing lipid leaflets. Depending on the lipid composition, these interactions lead to phase separation and formation of cholesterol crystals. The cholesterol and ceramide/cholesterol mixed phases were further characterized at 37°C by immunolabeling with specific antibodies recognizing ordered molecular arrays of cholesterol. Previous studies have shown that cholesterol may nucleate in artificial membranes to form thick two-dimensional bilayer crystals. The study herein demonstrates further growth of cholesterol into three-dimensional crystals. We believe that these results may provide further insight into the formation of cholesterol crystals in early stages of atherosclerosis inflammation.

Orientation and conformation of lipids in crystals of transmembrane proteins

Orientational order parameters and individual dihedral torsion angles are evaluated for phospholipid and glycolipid molecules that are resolved in X-ray structures of integral transmembrane proteins in crystals. The order parameters of the lipid chains and glycerol backbones in protein crystals are characterised by a much wider distribution of orientational order than is found in fluid lipid bilayers and reconstituted lipid-protein membranes. This indicates that the lipids that are resolved in crystals of membrane proteins are mostly not representative of the entire lipid-protein interface. Much of the chain configurational disorder of the membrane-bound lipids in crystals arises from C-C bonds in energetically disallowed skew conformations. This suggests configurational heterogeneity of the lipids at a single binding site: eclipsed conformations occur also in the glycerol backbone torsion angles and the C-C torsion angles of the lipid head groups. Conformations of the lipid glycerol backbone in protein crystals are not restricted to the gauche C1-C2 rotamers found invariably in phospholipid bilayer crystals. Lipid head-group conformations in the protein crystals also do not conform solely to the bent-down conformation, with gauche-gauche configuration of the phosphodiester, that is characteristic of phospholipid bilayer membranes. Stereochemical violations in the protein-bound lipids are evidenced by ester carboxyl groups in non-planar configurations, and even in the cis configuration. Some lipids have the incorrect enantiomeric configuration of the glycerol backbone, and many of the branched methyl groups in the phytanyl chains associated with bacteriorhodopsin have the incorrect S configuration.

Bilayer crystals of charged magnetic dipoles: Structure and phonon spectrum

We study the structure and phonon spectrum of a two-dimensional bilayer system of classical charged dipoles oriented perpendicular to the plane of the layers for equal density in each layer. This system can be tuned through six different crystalline phases by changing the interlayer separation or the charge and/or dipole moment of the particle. The presence of the charge on the dipole particles is responsible for the nucleation of five staggered phases and a disordered phase which are not found in the magnetic dipole bilayer system. These extra phases are a consequence of the competition between the repulsive Coulomb and the attractive dipole interlayer interaction. We present the phase diagram and determine the order of the phase transitions. The phonon spectrum of the system was calculated within the harmonic approximation, and a nonmonotonic behavior of the phonon spectrum is found as a function of the effective strength of the interparticle interaction. The stability of the different phases is determined.

Crystallization and Melting Behavior of Monodisperse Oligomers of ϵ-Caprolactone

Monodisperse ϵ-caprolactone (CL) oligomers with different end groups (t-butyldimethylsilyl, benzyl, hydroxyl, and carboxylic acid) and different numbers of repeating units (4–64) have been studied by differential scanning calorimetry and small-angle X-ray scattering (SAXS) in order to gather information regarding the melting temperature, long period, and melting enthalpy. Oligomers crystallized at their maximum temperatures (different for the different oligomers) to full crystallinity yielded extended-chain crystals for oligomers with 4, 8, and 16 repeating units with the important exception of the oligomers with four and eight repeating units and hydroxyl and benzyl end groups that showed double-layer crystals. Oligomers with 32 and 64 repeating units exhibited remarkably stable once-folded (32-mer) and thrice-folded (64-mer) crystals. Only the oligomer with 16 repeating units showed two crystallization temperature regimes resulting in once-folded crystals (low temperatures) and extended-chain crystals (high temperatures). The end groups had a profound effect on the structures. Hydrogen-bonding groups promoted the formation of crystal bilayers and led to a very high melting enthalpy (150 J g−1) exceeding the melting enthalpy of 100% crystalline poly (ϵ-caprolactone). The bulky end groups, in particular t-butyldimethylsilyl, reduced the crystallinity and favored chain tilting and probably preventing the unfolding of crystal stems in the oligomers with 32 and 64 repeating units. Melting temperatures of mature crystals obeyed a linear relationship with inverse CL stem length. The intercept (equilibrium melting temperature) was in the range of 350 to 357 K.

Unintentional doping induced splitting of G peak in bilayer graphene

Raman characterizations show the G peak of an unintentional doped single crystal bilayer graphene (BLG) splits into two peaks: S and AS peaks. From the relative shift between S and AS peaks, the doping concentration is estimated to be from 8.8 × 1012 cm−2 to 2 × 1013 cm−2, as in the same order of that in monolayer graphene prepared under the same condition. The dopants distribute relatively homogeneously in a 0.7 mm× 0.3 mm large BLG judged through the G peak splitting. The 2D peak of heavy doped BLG can only be deconvoluted into three peaks, corresponding to 2D1B, 2D1A, and 2D2A peaks.

Liquid to quasicrystal transition in bilayer water

The phase behavior of confined water is a topic of intense and current interest due to its relevance in biology, geology, and materials science. Nevertheless, little is known about the phases that water forms even when confined in the simplest geometries, such as water confined between parallel surfaces. Here we use molecular dynamics simulations to compute the phase diagram of two layers of water confined between parallel non hydrogen bonding walls. This study shows that the water bilayer forms a dodecagonal quasicrystal, as well as two previously unreported bilayer crystals, one tiled exclusively by pentagonal rings. Quasicrystals, structures with long-range order but without periodicity, have never before been reported for water. The dodecagonal quasicrystal is obtained from the bilayer liquid through a reversible first-order phase transition and has diffusivity intermediate between that of the bilayer liquid and ice phases. The water quasicrystal and the ice polymorphs based on pentagons are stabilized by compression of the bilayer and are not templated by the confining surfaces, which are smooth. This demonstrates that these novel phases are intrinsically favored in bilayer water and suggests that these structures could be relevant not only for confined water but also for the wetting and properties of water at interfaces.

Spectral features due to inter-Landau-level transitions in the Raman spectrum of bilayer graphene

We investigate the contribution of the low-energy electronic excitations toward the Raman spectrum of bilayer graphene for the incoming photon energy $\ensuremath{\Omega}\ensuremath{\gtrsim}1\text{ }\text{eV}$. Starting with the four-band tight-binding model, we derive an effective scattering amplitude that can be incorporated into the commonly used two-band approximation. Due to the influence of the high-energy bands, this effective scattering amplitude is different from the contact interaction amplitude obtained within the two-band model alone. We then calculate the spectral density of the inelastic light scattering accompanied by the excitation of electron-hole pairs in bilayer graphene. In the absence of a magnetic field, due to the parabolic dispersion of the low-energy bands in a bilayer crystal, this contribution is constant and in doped structures has a threshold at twice the Fermi energy. In an external magnetic field, the dominant Raman-active modes are the ${n}^{\ensuremath{-}}\ensuremath{\rightarrow}{n}^{+}$ inter-Landau-level transitions with crossed polarization of in/out photons. We estimate the quantum efficiency of a single ${n}^{\ensuremath{-}}\ensuremath{\rightarrow}{n}^{+}$ transition in the magnetic field of 10 T as ${I}_{{n}^{\ensuremath{-}}\ensuremath{\rightarrow}{n}^{+}}\ensuremath{\sim}{10}^{\ensuremath{-}12}$.

Nanocomposites of silver nanoparticle and dinonylnaphthalene disulfonic acid‐doped thermoreversible polyaniline gel

AbstractSilver/polyaniline‐dinonylnaphthalene disulfonic acid (PANI‐DNNDSA) gel nanocomposites are prepared from the reduction of silver salt by polyaniline in formic acid medium. Scanning electron micrographs (SEM) indicate the presence of three‐dimensional fibrillar network structure and the silver nanoparticles remain dispersed within the PANI‐DNNDSA fibrillar network. Differential scanning calorimetric (DSC) study shows reversible first‐order phase transition characterizing the composite to behave as a thermoreversible gel. Transmission electron micrographs (TEM) show a decrease of nanoparticle size with increasing AgNO3 concentration. Wide angle X‐ray scattering (WAXS) patterns show lamellar structure in the gel as well as in the gel metal nanocomposites (GMNCs) and the two melting peaks in the DSC patterns correspond to the melting of monolayer and bilayer crystals produced from the interdigitation of DNNDSA tails anchored from PANI chains within the PANI lamella. The above melting points are greater in the GMNCs than that of pure gel indicating the formation of complex melting thermogram with crystallites produced from the anchored surfactants tails at the surface of Ag nanoparticles. The GMNCs show a higher thermal stability than that of pure PANI‐DNNDSA gel. PANI‐DNNDSA gel has an emission peak at 354 nm but fluorescence quenching occurs in the GMNCs and the emission peak becomes red shifted. Also in the UV–vis spectra the π band‐polaron band transition peak shows a red shift and the DC conductivity increases with increasing Ag nanoparticle concentration in the GMNCs. The current (I)–voltage (V) characteristic curves indicate Ohmic nature of conductivity of the gel and the current at the same voltage increases appreciably with increasing Ag nanoparticle concentration. These GMNCs are easily processible due to its thermoreversible nature. So, an easily processible, thermally stable and highly conducting DNNDSA‐doped PANI‐Ag gel nanocomposite with interesting photoluminescent property has been successfully developed suitable for optoelectronic applications. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers

Preferential location of prilocaine and etidocaine in phospholipid bilayers: A molecular dynamics study

In this work, we report a 20-ns constant pressure molecular dynamics simulation of the uncharged form of two amino–amide local anesthetics (LA), etidocaine and prilocaine, present at 1:3 LA:lipid, molar ratio inside the membrane, in the hydrated liquid crystal bilayer phase of 1-palmitoyl-2-oleoyl- sn-glycero-3-phosphatidylcholine (POPC). Both LAs induced lateral expansion and a concomitant contraction in the bilayer thickness. A decrease in the acyl chain segment order parameter, − S CD, compared to neat bilayers, was also observed. Besides, both LA molecules got preferentially located in the hydrophobic acyl chains region, with a maximum probability at ∼12 and ∼10 Å from the center of the bilayer for prilocaine and etidocaine, respectively.