Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups.

Zero-order waveplates are widely used in the manufacture of laser polarizer waves, which are important in polarimetry and the laser industry. However, there are still challenges in designing deep-ultraviolet (DUV) waveplate materials that satisfy large band gaps and small optical anisotropy simultaneously. Herein, three cases of aluminum sulfate fluorides: Na2AlSO4F3, Li4NH4Al(SO4)2F4, and Li6K3Al(SO4)4F4, with novel [AlSO4F3] layers or isolated [AlS2O8F4] trimers were designed and synthesized by the rational assembly of [AlO2F4] and [SO4] groups through a hydrothermal method. Experiments and theoretical calculations imply that these three possess short cutoff edges (λ < 200 nm) and small birefringence (0.0014-0.0076 @ 1064 nm), which fulfils the prerequisite for potential DUV zero-order waveplate materials. This work extends the exploration of DUV zero-order waveplate materials to the aluminum sulfate fluoride systems.

The design of highly conductive and stretchable polymer conductors with low-load nanoparticles.

Highly conductive and stretchable polymer conductors fabricated from conductive fillers and stretchable polymers are urgently needed in flexible electronics, implants, soft robotics, etc. However, polymer conductors encounter the conductivity-stretchability dilemma, in which high-load fillers needed for high conductivity always result in the stiffness of materials. Herein, we propose a new design of highly conductive and stretchable polymer conductors with low-load nanoparticles (NPs). The design is achieved by the self-assembly of surface-modified NPs to efficiently form robust conductive pathways. We employ computer simulations to elucidate the self-assembly of the NPs in the polymer matrices under equilibrium and tensile states. The conductive pathways retain 100% percolation probability even though the loading of the NPs is lowered to ∼2% volume. When the tensile strain reaches 400%, the percolation probability of the ∼2% NP system is still greater than 25%. The theoretical prediction suggests a way for advancing flexible conductive materials.

First Principles Study of the Photoelectric Properties of Alkaline Earth Metal (Be/Mg/Ca/Sr/Ba)-Doped Monolayers of MoS2.

The energy band structure, density of states, and optical properties of monolayers of MoS2 doped with alkaline earth metals (Be/Mg/Ca/Sr/Ba) are systematically studied based on first principles. The results indicate that all the doped systems have a great potential to be formed and structurally stable. In comparison to monolayer MoS2, doping alkaline earth metals results in lattice distortions in the doped system. Therefore, the recombination of photogenerated hole-electron pairs is suppressed effectively. Simultaneously, the introduction of dopants reduces the band gap of the systems while creating impurity levels. Hence, the likelihood of electron transfer from the valence to the conduction band is enhanced, which means a reduction in the energy required for such a transfer. Moreover, doping monolayer MoS2 with alkaline earth metals increases the static dielectric constant and enhances its polarizability. Notably, the Sr-MoS2 system exhibits the highest value of static permittivity, demonstrating the strongest polarization capability. The doped systems exhibit a red-shifted absorption spectrum in the low-energy region. Consequently, the Be/Mg/Ca-MoS2 systems demonstrate superior visible absorption properties and a favorable band gap, indicating their potential as photo-catalysts for water splitting.

Strain-tunable magnetic and electronic properties of a CuCl3 monolayer.

Recently, theoretical search has found that a two-dimensional CuCl3 monolayer is a ferromagnetic semiconductor. Here, we apply density functional theory to study its geometrical structure, magnetic and electronic properties under the influence of a biaxial strain ε. It is found that the CuCl3 monolayer exhibits ferromagnetic ordering at the ground state with ε = 0 and its Curie temperature increases monotonously with respect to the biaxial strain, which can be increased to about 100 K at 10% tensile strain. When a compressive strain of about 6.8% is applied, a transition from the ferromagnetic to the antiferromagnetic state occurs. In addition to the transition of the magnetic ground state, the electronic band gaps of spin-up and spin-down electrons undergo direct-indirect and indirect-direct-indirect transitions at the tensile strains, respectively. The tunable magnetic and electronic properties investigated in this work are helpful in understanding the magnetism in the CuCl3 monolayer, which is useful for the design of spintronic devices based on ferromagnetic semiconductors.

Effects of nanopore size on the flow-induced star polymer translocation.

We study the effects of the nanopore size on the flow-induced capture of the star polymer by a nanopore and the afterward translocation, using a hybrid simulation method that couples point particles into a fluctuating lattice-Boltzmann fluid. Our simulation demonstrates that the optimal forward arm number decreases slowly with the increase of the length of the nanopore. Compared to the minor effect of the length of the nanopore, the optimal forward arm number obviously increases with the increase of the width of the nanopore, which can clarify the current controversial issue for the optimal forward arm number between the theory and experiments. In addition, our results indicate that the critical velocity flux of the star polymer is independent of the nanopore size. Our work bridges the experimental results and the theoretical understanding, which can provide comprehensive insights for the characterization and the purification of the star polymers.

KRb2(NO3)2Cl: a new birefringent crystal exhibiting a perovskite-related framework and a short cutoff edge.

The combination of π-conjugated groups [NO3] and Cl-centered polyhedra generates a new birefringent crystal with a perovskite-related framework, KRb2(NO3)2Cl, which is the first alkali metal nitrate chloride synthesized by a mild hydrothermal method. It crystallizes in the orthorhombic space group pbam (no. 55). In addition, KRb2(NO3)2Cl crystals with dimensions up to 7 × 1.5 × 1 mm3 were grown. Notably, KRb2(NO3)2Cl has a short UV cut-off edge (below 228 nm) and a significantly enhanced birefringence (Δn = 0.084 at 1064 nm). Theoretical calculations indicate that the birefringence enhancement mainly derives from π-conjugated [NO3] plane triangles.

Ba2Zn2B6O13: coplanar [B2O5] in unnoted U-shaped [B6O13] groups achieving large birefringence.

Currently, π-conjugated [B2O5] moieties are rarely studied for designing deep-UV birefringent crystals. Here, we report a new deep-UV birefringent crystal Ba2Zn2B6O13 with a deep-UV cut-off edge of 190 nm and large birefringence (Δn = 0.085@ 532 nm), indicating that it can be used as the birefringent material in the DUV area. The first-principles calculation analyses suggest that its large birefringence mainly originates from the coplanar [B2O5] dimers in the unnoted U-shaped [B6O13].

RbMo2P3O14 with large birefringence mainly induced by highly distorted [MoO6] in uncommon [Mo2P3O14]∞ layers.

The introduction of d0 transition metal Mo6+ cations into a phosphate generates a new acentric molybdophosphate, RbMo2P3O14. It shows uncommon [Mo2P3O14]∞ layers composed of isolated [MoO6] octahedra and [P3O10] groups. To the best of our acknowledge, it exhibits the largest birefringence (a calculated value of 0.166 at 546 nm) among reported molybdophosphates. In addition, it also possesses a shorter UV cut-off edge (about 250 nm) than other molybdates and molybdophosphates, indicating that it can be used as a birefringent crystal in the UV optical region. First-principles electronic structure analysis suggests that the large birefringence mainly originates from highly distorted [MoO6].

Theory of relaxor-ferroelectricity.

Relaxor-ferroelectrics are fascinating and useful materials, but the mechanism of relaxor-ferroelectricity has been puzzling the scientific community for more than 65 years. Here, a theory of relaxor-ferroelectricity is presented based on 3-dimensional-extended-random-site-Ising-model along with Glauber-dynamics of pseudospins. We propose a new mean-field of pseudospin-strings to solve this kinetic model. The theoretical results show that, with decreasing pseudospin concentration, there are evolutions from normal-ferroelectrics to relaxor-ferroelectrics to paraelectrics, especially indicating by the crossovers from, (a) the sharp to diffuse change at the phase-transition temperature to disappearance in the whole temperature range of order-parameter, and (b) the power-law to Vogel-Fulcher-law to Arrhenius-relation of the average relaxation time. Particularly, the calculated local-order-parameter of the relaxor-ferroelectrics gives the polar-nano-regions appearing far above the diffuse-phase-transition and shows the quasi-fractal characteristic near and below the transition temperature. We also provide a new mechanism of Burns-transformation which stems from not only the polar-nano-regions but also the correlation-function between pseudospins, and put forward a definition of the canonical relaxor-ferroelectrics. The theory accounts for the main facts of relaxor-ferroelectricity, and in addition gives a good quantitative agreement with the experimental results of the order-parameter, specific-heat, high-frequency permittivity, and Burns-transformation of lead magnesium niobate, the canonical relaxor-ferroelectric.

Large optical polarizability causing positive effects on the birefringence of planar-triangular BO3 groups in ternary borates.

The structure-property relationship of photoelectric functional materials has been recognized as a hot topic. The study of the inner link between the band gaps and birefringence of optical materials is extremely crucial for the design and creation of novel optical devices, but still remains rather unexplored. In this work, taking a series of borates with only planar-triangular BO3 groups, α-/ß-TM3(BO3)2 (TM = Zn, Cd), Cd2B2O5, and M3(BO3)2 (M = Hg, Mg, Ca, Sr) as the research subject, the comprehensive relationship between their electronic structures and linear optical properties has been systematically investigated. Through combining experimental measurements and theoretical calculations, the effect of optical polarizability on the birefringence of these borates was clarified. Based on the present discussion, the relationship between the O (2p) bandwidth of the highest valence band and the HSE06 band gaps is opposite. Meanwhile, a method involving the determination of so-called optical permittivity Δε to evaluate the magnitude of birefringence Δn is found to be feasible. A large Δε makes a positive contribution to Δn. In addition, the experimentally measured band gaps and IR vibrations are in good agreement with theoretical results for the compounds α-Cd3(BO3)2 and Cd2B2O5.

Enthalpy-driven self-assembly of amphiphilic Janus dendrimers into onion-like vesicles: a Janus particle model.

Synthetic vesicles of amphiphilic Janus dendrimers are known as dendrimersomes. The understanding of the conditions and formation mechanism of dendrimersomes is meaningful for further controlling the structures. Herein, the characteristics of the self-assembly of amphiphilic Janus dendrimer/water solutions into unilamellar and onion-like dendrimersomes are studied by molecular dynamics simulations via a spherical single-site Janus particle model. The model with two distinct surfaces, one hydrophobic side and another hydrophilic side, describes the amphiphilic nature of Janus dendrimers. By reducing the dendrimers with complex architectures to be simple Janus particles, we investigate the concentration-dependent self-assembled structures as well as the enthalpy-driven formation process of onion-like dendrimersomes, in contrast to the entropy-mediated self-assembly of amphiphilic flexible chains. Three typical equilibrium morphologies including linear micelles, lamellar structures and vesicles are found upon varying the Janus balance and dendrimer concentration. It is observed that the dendrimersomes consisting of the dendrimers with neglectable molecular configuration entropy become very stable, which agrees well with experimental observation. Specifically, different from many lipidsomes and polymersomes which can spontaneously merge, the size of dendrimersomes will not increase through mutual fusion once the well-defined onion-like structure is formed. Moreover, the discharge of water is achieved by water diffusion in our simulations, instead of in the "peeling-one-onion-layer-at-a-time" fashion. Our study combined with the previous ones using flexible chain models could depict a complete picture of dendrimersomes in favor of their applications in drug and gene delivery.