Surface-sensitive electronic structure of kagome superconductor CsV_(3)Sb_(5)

We systematically study the electronic structure of a kagome superconductor CsV_(3)Sb_(5)at different temperatures coveringboth its charge density wave state and normal state with angle-resolved photoemission spectroscopy.We observe thatthe V-shaped band aroundГshows three different behaviors,referred to as a/a',βandγ,mainly at different temperatures.Detailed investigations confirm that these bands are all from the same bulk Sb-p_(z)origin,but they are quite sensitiveto the sample surface conditions mainly modulated by temperature.Thus,the intriguing temperature dependent electronicbehavior of the band nearГis affected by the sample surface condition,rather than intrinsic electronic behavior originatingfrom the phase transition.Our result systematically reveals the confusing electronic structure behavior of the energy bandsaroundГ,facilitating further exploration of the novel properties in this material.

Discovery of superhard materials via CALYPSO methodology

The study of superhard materials plays a critical role in modern industrial applications due to their widespread applications as cutting tools, abrasives, exploitation drills, and coatings. The search for new superhard materials with superior performance remains a hot topic and is mainly considered as two classes of materials:(i) the light-element compounds in the B-C-N-O(-Si) system with strong and short covalent bonds, and(ii) the transition-element light-element compounds with strong covalent bonds frameworks and high valence electron density. In this paper, we review the recent achievements in the prediction of superhard materials mostly using the advanced CALYPSO methodology. A number of novel, superhard crystals of light-element compounds and transition-metal borides, carbides, and nitrides have been theoretically identified and some of them account well for the experimentally mysterious phases. To design superhard materials via CALYPSO methodology is independent of any known structural and experimental data, resulting in many remarkable structures accelerating the development of new superhard materials.

Novel Boron Nitride Polymorphs with Graphite-Diamond Hybrid Structure

Both boron nitride(BN)and carbon(C)have sp,sp^(2)and sp^(3)hybridization modes,thus resulting in a variety of BN and C polymorphs with similar structures,such as hexagonal BN(hBN)and graphite,cubic BN(cBN)and diamond.Here,five types of BN polymorph structures are proposed theoretically,inspired by the graphite-diamond hybrid structures discovered in a recent experiment.These BN polymorphs with graphite-diamond hybrid structures possess excellent mechanical properties with combined high hardness and high ductility,and also exhibit various electronic properties such as semi-conductivity,semi-metallicity,and even one-and two-dimensional conductivity,differing from known insulators hBN and cBN.The simulated diffraction patterns of these BN hybrid structures could account for the unsolved diffraction patterns of intermediate products composed of so-called“compressed hBN”and diamond-like BN,caused by phase transitions in previous experiments.Thus,this work provides a theoretical basis for the presence of these types of hybrid materials during phase transitions between graphite-like and diamond-like BN polymorphs.

Design of a Class of New sp^(2)-sp^(3)Carbons Constructed by Graphite and Diamond Building Blocks

The sp^(2)–sp^(3)-hybridized carbon allotropes with the advantage of two hybrid structures possess rich and fascinating electronic and mechanical properties and they have received long-standing attention.We design a class of versatile sp^(2)–sp^(3)carbons composed of graphite and diamond structural units with variable sizes.This class of sp^(2)–sp^(3)carbons is energetically more favorable than graphite under high pressure,and their mechanical and dynamical stabilities are further confirmed at ambient pressure.The calculations of band structure and mechanical properties indicate that this class of sp^(2)–sp^(3)carbons not only exhibits peculiar electronic characteristics adjusted from semiconducting to metallic nature but also presents excellent mechanical characteristics,such as superhigh hardness and high ductility.These sp^(2)–sp^(3)carbons have desirable properties across a broad range of potential applications.

范德华材料Ta_(2)Ni_(3)Te_(5)中巨大的面内振动和输运各向异性

目前,Ta_(2)M3Te_(5)(M=Ni,Pd)层状范德华化合物可承载各种奇异电子态,且具有表现出非平凡输运现象的诱人潜力,因而重新引起人们的兴趣.其特征有Luttinger液体、量子自旋霍尔效应、高阶拓扑结构和超导电性.本文中,我们报道了单晶Ta_(2)Ni_(3)Te_(5)的合成,并揭示了其在每个具有准一维键合特征的层内的多重平面内各向异性.我们的技术结合了偏振拉曼光谱、角度分辨光电发射光谱、第一性原理计算和电/磁输运测量的能力.链状低对称层状结构的声子振动产生了高度各向异性的拉曼响应,不同的链内和链间键合特性导致电子带和声学声子的各向异性色散,这共同导致[100]和[001]方向之间的巨大平面内迁移率各向异性(2000%).这一结果与我们的电输运和霍尔效应测量结果相符.因此,沿不同平面内方向的输运行为也表现出不同的温度和磁场依赖性.本工作揭示的丰富的面内各向异性表明,Ta_(2)Ni_(3)Te_(5)是探索新型二维各向异性电子动力学的一个很有前途的平台,在下一代纳米电子器件中具有潜在的应用前景.

Surface vitrification of carbon by laser treatment: Insights of glass formation from molecular dynamics

Microstructural modification of carbon materials,such as carbon fibers(Cf)and pyrolytically deposited carbon,is important for engineering applications.However,the regulation of these materials is not an effortless task.To understand the impacts of thermal spikes from pulsed laser processing on the structural adaptation of amorphous carbon(a-C),we performed melt quenching by molecular dynamics(MD)simulations.Our results confirm that the vitrification behavior of carbon can be tuned by adjusting the cooling rate(R),which is controlled by the thermal spikes of laser processing.Moreover,we set up a two-step way to locate the critical cooling rate(R_(c))of monoatomic carbon,which is refined by the sharp change in the environmental similarity parameter.Using this novel technique,we demonstrate that the ordering degree and the local atomic motif can be largely modified by going across a bar of 100 K/ps,which is extracted as the critical cooling rate to ensure the complete amorphization of carbon.This approach provides a criterion for both experimentally processing and theoretically simulating a-C structures.Therefore,this work provides guidelines on how to tune the amorphous carbon structures of engineering materials and provides an outlook for the wonderland of amorphous carbon materials.

Ultrafine-grained high-entropy zirconates with superior mechanical and thermal properties

Ultrafine-grained(Sm_(0.2)Gd_(0.2)Dy_(0.2)Er_(0.2)Yb_(0.2))_(2)Zr_(2)O_(7)high-entropy zirconates with single fluorite structure have been fabricated by high-pressure sintering of the self-synthesized nanopowders for the first time.The as-sintered samples exhibit a good microstructure with a grain size of 220 nm and a relative density of 96.8%,which yield excellent comprehensive mechanical properties with a high Vickers hardness of 12.5 GPa and a high fracture toughness of 3.4 MPa·m1/2.In addition,the as-sintered samples possess a good thermostability with the grain growth rate of 30 nm/h,and a low thermal conductivity of 1.57 W·m^(-1)·℃^(-1)at room temperature.The superior mechanical and thermal properties are primarily attributed to the“high-entropy”and grain-refinement effects and good interface bonding.

Nanocrystalline high-entropy hexaboride ceramics enable remarkable performance as thermionic emission cathodes

The development of high-entropy borides with combined structural and functional performance holds untold scientific and technological potential,yet relevant studies have been rarely reported.In this work,we report nanocrystalline(La_(0.25)Ce_(0.25)Nd_(0.25)Eu_(0.25))B6 high-entropy rare-earth hexaboride(HEReB6-1)ceramics fabricated through the high-pressure sintering of self-synthesized nanopowders for the first time.The as-fabricated samples exhibited a highly dense(96.3%)nanocrystalline(94 nm)microstructure with major(001)fiber textures and good grain boundaries without any impurities,resulting in a remarkable mechanical,electrical,and thermionic emission performance.The results showed that the samples possessed outstanding comprehensive mechanical properties and a high electrical resistivity from room temperature to high temperatures;these were greater than the average values of corresponding binary rare-earth hexaborides,such as a Vickers hardness of 23.4±0.6 GPa and a fracture toughness of 3.0±0.4 MPa•m^(1/2)at room temperature.More importantly,they showed high emission current densities at elevated temperatures,which were higher than the average values of the corresponding binary rare-earth hexaborides.For instance,the maximum emission current density reached 48.3 A•cm^(−2)at 1873 K.Such superior performance makes the nanocrystalline HEReB6-1 ceramics highly suitable for potential applications in thermionic emission cathodes.

基于二十面体的新型B_(12)CN和B_(13)CN结构的第一性原理研究

以二十面体为基元的富硼化合物具有复杂多样的电子和机械性能.在本工作中,我们采用粒子群优化结构预测方法结合第一性原理计算,首次对二十面体基元的三元B_(12)CN和B_(13)CN化合物的晶体结构和性质进行了全面系统的研究.我们搜索得到了B_(13)CN和B_(12)CN化合物的新结构,其空间群均为Cmc21,与α-B的变体结构相比,新结构具有更优异的热力学稳定性.B_(12)CN的热力学稳定性和机械性能均稍逊于B_(13)CN.此外,B含量的微小差异造成了B_(12)CN与B_(13)CN两种三元化合物迥异的电学特性,即B_(13)CN具有半导体特性,而B_(12)CN具有空穴型导电特性.此外,在B_(12)CN与B_(13)CN系列新结构的拉伸过程中,由于二十面体的连续破坏和二十面体之间的连续断键造成的应力再增强、结构多级破坏和类蠕变变形等特殊变形机制也同样被揭示.

The rise of plastic deformation in boron nitride ceramics

Ceramics are bonded by ionic or covalent bonds,with very limited slip systems for dislocation nucleation and movement[1].The poor deformability and natural brittleness are the major drawbacks of ceramics,especially when compared with metals.Under stress,ceramics tend to fracture before noticeable plastic deformation takes place.Cracks occur and propagate rapidly in ceramics subjected to stress much lower than the theoretical strength[2].As a result,ceramics can only endure very small strains(<1%),absorb limited mechanical energy,and display poor toughness[3].Moreover,microstructure imperfections in ceramics may decrease the toughness even further.Due to the lack of significant plastic deformation capacity for ceramic materials,the catastrophic failures without warning are easy to happen under stress which critically increases the unreliability of ceramics in the applications as structural materials.

Broadband photodetector of high quality SbS nanowire grown by chemical vapor deposition

Low dimensional semiconductors can be used for various electronic and optoelectronic devices because of their unique structure and property.In this work,one-dimensional Sb2 S3 nanowires(NWs)with high crystallinity were grown via chemical vapor deposition(CVD)technique on SiO2/Si substrates.The Sb2 S3 NWs exhibited needle-like structures with inclined cross-sections.The lengths of Sb2S3 nanowires changed from 7 to 13μm.The photodetection properties of Sb2 S3 nanowires were comprehensively and systematically characterized.The Sb2S3 photodetectors show a broadband photoresponse ranging from ultraviolet(360 nm)to near-infrared(785 nm).An excellent specific detectivity of 2.1×10^(14)Jones,high external quantum efficiency of 1.5×10^(4)%,sensitivity of 2.2×10^(4)cm^(2)W^(-1)and short response time of less than 100 ms was achieved for the Sb2 S3 NW photodetectors.Moreover,the Sb2S3 NWs showed outstanding switch cycling stability that was beneficial to the practical applications.The high-quality Sb2S3 nanowires fabricated by CVD have great application potential in semiconductor and optoelectronic fields.

Extraordinary high-temperature mechanical properties in binder-free nanopolycrystalline WC ceramic

From the perspective of high-temperature applications,materials with excellent high-temperature mechanical properties are always desirable.The present work demonstrates that the binder-free nanopolycrystalline WC ceramic with an average grain size of 103 nm obtained by high-pressure and hightemperature sintering exhibits excellent mechanical properties at both room temperature and high temperature up to 1000℃.Specifically,the binder-free nanopolycrystalline WC ceramic still maintains a considerably high Vicker hardness H_(V)of 23.4 GPa at 1000℃,which is only 22%lower than the room temperature H_(V).This outstanding thermo-mechanical stability is superior to that of typical technical ceramics,e.g.SiC,Si_(3)N_(4),Al_(2)O_(3),etc.Nanocrystalline grains with many dislocations,numerous low-energy,highly stableΣ2 grain boundaries,and a relatively low thermal expansion coefficient,are responsible for the observed outstanding high-temperature mechanical properties.

Small onion-like BN leads to ultrafine-twinned cubic BN

Nanotwinned cubic boron nitride(nt-cBN) with remarkable hardness, toughness, and stability has attracted widespread attention due to its distinct scientific and industrial importance. The key for nt-cBN synthesis is to adopt an onion-like BN(oBN) nano-precursor and induce phase transition under high pressure. Here, we found that the size change of oBN used greatly affected the mechanical performance of products. With the precursor size decreasing from^320 to 90 nm, the Vickers hardness of nanostructured products improved from 61 to 108 GPa, due to the fact that large oBN nanoparticles possessed more flattened, orderly and graphite-like shell layers, in sharp contrast to the highly wrinkled and imperfect layers in small-diameter nanoparticles, thus resulting in the apparent reduction of ultrafinetwin substructure in the synthetic products. This study reveals that only small oBN precursor could produce complete ultrafine nt-cBN with outstanding performance. A practical route was proposed to further improve the performance of this important material.

Enhanced thermoelectric performance of Na-doped Pb Te synthesized under high pressure

Despite an effective p-type dopant for PbTe, the low solubility of Na limits the fully optimization of thermoelectric properties of Na-doped PbTe. In this work, Na-doped PbTe was synthesized under high pressure. The formation of the desired rocksalt phase with substantially increased Na content leads to a high carrier concentration of 3.2×10^20 cm^-3 for Na0.03Pb0.97Te. Moreover, dense in-grain dislocations are identified from the microstructure analysis. Benefited from the improved power factor and greatly suppressed lattice thermal conductivity, the maximal ZT of 1.7 is achieved in the optimal Na0.03Pb0.97Te. Current work thus designates the advantage of high pressure in synthesizing PbTe-based thermoelectric materials.

Continuous strengthening in nanotwinned diamond

Strengths of nanograined(ng)and nanotwinned(nt)metals increase with decreasing grain size and twin thickness,respectively,until reaching a critical value,below which strength decreases.This behavior is known as the reverse Hall–Petch effect(RHPE),which has also been observed in nanograined cubic boron nitride(cBN)and diamond.Surprisingly,however,hardness of nt-cBN and nt-diamond increases continuously with decreasing twin thickness down to several nanometers,suggesting the absence of RHPE in these covalent materials.The mechanism responsible for such a behavior remains controversial.Here we investigate the strengthening mechanisms in ng-and nt-diamond using molecular dynamics and first-principles calculations.For ng-diamond,the competition between shuffle-set dislocation(SSD)and grain boundary atom motions gives rise to RHPE.For nt-diamond,SSDs remain dominant but their slips along twin boundaries energetically show no advantage over those along other slip planes.Twin domains are locked and mechanically stable,resisting SSD propagation and inhibiting RHPE.These findings provide new insights into the hardening mechanism of nanotwinned covalent materials.

Heat-treated glassy carbon under pressure exhibiting superior hardness,strength and elasticity

Glassy carbon(GC)is a type of non-graphitizing disordered carbon material at ambient pressure and high temperatures,which has been widely used due to its excellent mechanical properties.Here we report the changes in the microstructure and mechanical properties of GC treated at high pressures(up to 5 GPa)and high temperatures.The formation of intermediate sp2-sp3 phases is identified at moderate treatment temperatures before the complete graphitization of GC,by analyzing synchrotron X-ray diffraction,Raman spectra,and transmission electron microscopy images.The intermediate metastable carbon materials exhibit superior mechanical properties with hardness reaching up to 10 GPa and compressive strength reaching as high as 2.5 GPa,nearly doubling those of raw GC,and improving elasticity and thermal stability.The synthesis pressure used in this study can be achieved in the industry on a commercial scale,enabling the scalable synthesis of this type of strong,hard,and elastic carbon materials.

Hard nanocrystalline gold materials prepared via high-pressure phase transformation

As one of the important materials,nanocrystalline Au(n-Au)has gained numerous interests in recent decades owing to its unique properties and promising applications.However,most of the current n-Au thin films are supported on substrates,limiting the study on their mechanical properties and applications.Therefore,it is urgently desired to develop a new strategy to prepare nAu materials with superior mechanical strength and hardness.Here,a hard n-Au material with an average grain size of~40 nm is prepared by cold-forging of the unique Au nanoribbons(NRBs)with unconventional 4H phase under high pressure.Systematic characterizations reveal the phase transformation from 4H to face-centered cubic(fcc)phase during the cold compression.Impressively,the compressive yield strength and Vickers hardness(HV)of the prepared n-Au material reach~140.2 MPa and~1.0 GPa,which are 4.2 and 2.2 times of the microcrystalline Au foil,respectively.This work demonstrates that the combination of high-pressure cold-forging and the in-situ 4H-to-fcc phase transformation can effectively inhibit the grain growth in the obtained n-Au materials,leading to the formation of novel hard n-Au materials.Our strategy opens up a new avenue for the preparation of nanocrystalline metals with superior mechanical property.