二维材料最新研究进展

Research on two-dimensional(2D) materials has been explosively increasing in last seventeen years in varying subjects including condensed matter physics, electronic engineering, materials science, and chemistry since the mechanical exfoliation of graphene in 2004. Starting from graphene, 2D materials now have become a big family with numerous members and diverse categories. The unique structural features and physicochemical properties of 2D materials make them one class of the most appealing candidates for a wide range of potential applications. In particular, we have seen some major breakthroughs made in the field of 2D materials in last five years not only in developing novel synthetic methods and exploring new structures/properties but also in identifying innovative applications and pushing forward commercialisation. In this review, we provide a critical summary on the recent progress made in the field of 2D materials with a particular focus on last five years. After a brief backgroundintroduction, we first discuss the major synthetic methods for 2D materials, including the mechanical exfoliation, liquid exfoliation, vapor phase deposition, and wet-chemical synthesis as well as phase engineering of 2D materials belonging to the field of phase engineering of nanomaterials(PEN). We then introduce the superconducting/optical/magnetic properties and chirality of 2D materials along with newly emerging magic angle 2D superlattices. Following that, the promising applications of 2D materials in electronics, optoelectronics, catalysis, energy storage, solar cells, biomedicine, sensors, environments, etc. are described sequentially. Thereafter, we present the theoretic calculations and simulations of 2D materials. Finally, after concluding the current progress, we provide some personal discussions on the existing challenges and future outlooks in this rapidly developing field.

Origin of off-centering effect and the influence on heat transport in thermoelectrics

Recently,off-centering behavior has been discovered in a series of thermoelectric materials.This behavior indicates that the constituent atoms of the lattice displace from their coordination centers,leading to the locally distorted state and local symmetry breaking,while the material still retains its original crystallographic symmetry.This effect has been proved to be the root cause of ultralow thermal conductivity in off-centering materials,and is considered as an effective tool to regulate the thermal conductivity and improve the thermoelectric performance.Herein,we present a collection of recently discovered off-centering compounds,discuss their electronic origins and local coordination structures,and illuminate the underlying mechanism of the off-centering effect on phonon transport and thermal conductivity.This paper presents a comprehensive view of our current understanding to the off-centering effect,and provides a new idea for designing high performance thermoelectrics.

Lattice expansion enables interstitial doping to achieve a high average ZT in n-type PbS

Lead sulfide(PbS)presents large potential in thermoelectric application due to its earth-abundant S element.However,its inferior average ZT(ZTave)value makes PbS less competitive with its analogs PbTe and PbSe.To promote its thermoelectric performance,this study implements strategies of continuous Se alloying and Cu interstitial doping to synergistically tune thermal and electrical transport properties in n-type PbS.First,the lattice parameter of 5.93Åin PbS is linearly expanded to 6.03Åin PbS_(0.5)Se_(0.5)with increasing Se alloying content.This expanded lattice in Se-alloyed PbS not only intensifies phonon scattering but also facilitates the formation of Cu interstitials.Based on the PbS_(0.6)Se_(0.4)content with the minimal lattice thermal conductivity,Cu interstitials are introduced to improve the electron density,thus boosting the peak power factor,from 3.88μW cm^(−1)K^(−2)in PbS_(0.6)Se_(0.4)to 20.58μW cm^(−1)K^(−2)in PbS0.6Se0.4−1%Cu.Meanwhile,the lattice thermal conductivity in PbS_(0.6)Se_(0.4)−x%Cu(x=0-2)is further suppressed due to the strong strain field caused by Cu interstitials.Finally,with the lowered thermal conductivity and high electrical transport properties,a peak ZT~1.1 and ZTave~0.82 can be achieved in PbS_(0.6)Se_(0.4)−1%Cu at 300–773K,which outperforms previously reported n-type PbS.

构建准层状自空穴掺杂SnSe取向薄膜获得优异热电功率因子和输出功率密度

热电技术可以实现热能与电能的相互转换,其开发利用对于缓解能源危机具有重要意义.近10年来,SnSe因其潜在的高能量转换效率、绿色环保和低成本特性而备受关注.但SnSe的固有载流子浓度低(约10~(17)cm^(-3)),导致其功率因子偏低,从而限制了SnSe基器件的输出功率密度.因此,探索新的载流子浓度优化策略对于SnSe的应用至关重要.此外,与三维块体相比,二维薄膜更易和现代半导体工艺相兼容,在热电微纳米器件的构筑和应用方面具有独特优势.本文报道了一种利用非原位硒化技术,通过电荷转移和自空穴掺杂效应来优化a轴取向SnSe基薄膜的载流子浓度.当硒化时间为20 min时,薄膜载流子浓度可提高至10~(18)cm^(-3)数量级,形成了准层状的自空穴掺杂SnSe基薄膜,其功率因子在600 K时达到了5.9μW cm^(-1)K^(-2).由硒化处理的SnSe基取向薄膜构筑的热电发电机在50和90 K的温差下分别具有约83、838μW cm^(-2)的超高功率密度.非原位硒化技术可以有效提高SnSe基薄膜的载流子浓度,为其他热电材料性能优化提供了一种新策略.

Enhancing thermoelectric performance of n-type AgBi_(3)S_(5)through synergistically optimizing the effective mass and carrier mobility

AgBi_(3)S_(5) is a new n-type thermoelectric material that is environmentally friendly and composed of elements of earth-abundant,non-toxic and high performance-cost ratio.This compound features an intrinsically low thermal conductivity derived from its complex monoclinic structure.However,the terrible electrical transport properties greatly limited the improvement of thermoelectric performance.Most previous studies considered that carrier concentration is the main reason for low electrical conductivity and focused on improving carrier concentration by aliovalent ion doping.In this work,we found that the critical parameter that restricts the electric transport performance of AgBi_(3)S_(5)was the extremely low carrier mobility instead of the carrier concentration.According to the Pisarenko relationships and density functional theory calculations,Nb doping can sharpen the conduction band of AgBi_(3)S_(5),which contributes to reducing the effective mass and improving the carrier mobility.With a further increase of the Nb doping content,the conduction band convergence can enlarge the effective mass and preserve the carrier mobility.Combined with the decrease in lattice thermal conductivity due to the intensive phone scattering,a maximum ZT value of~0.50 at 773 K was achieved in Ag_(0.97)Nb_(0.03)Bi_(3)S_(5),which was~109.6%higher than that of pure AgBi3S5.This work will stimulate the new exploration of high-performance thermoelectric materials in ternary metal sulfides.

Realizing p-type performance in low-thermal-conductivity BiSbSe_(3) via lead doping

BiSbSe_(3) is an intrinsic n-type thermoelectric material,which attracts a lot of research interest due to its low lattice thermal conductivity and multiple band structure,and it exhibits excellent thermoelectric properties in the midtemperature region.However,there is little research on p-type BiSbSe_(3).This work realized the successful preparation of p-type BiSbSe_(3) through Pb doping.The thermoelectric transport properties of Pb-doped p-type BiSbSe_(3)were investigated.Pb doping could further reduce the thermal conductivity of BiSbSe_(3).All Pb-doped samples exhibited and maintained stable p-type transmissionthroughout the working temperature range(300-723 K).This work proves that Pb can be successfully used as a p-type dopant for BiSbSe_(3).

Comparison between Bilateral and Unilateral Sudden Sensorineural Hearing Loss

Background：Bilateral sudden sensorineural hearing loss （BSSHL） is rare and assumed to be a different clinical entity compared to unilateral SSHL （USSHL）.This study examined the differences between the idiopathic BSSHL and USSHL.Methods：Forty-six sequential BSSHL patients （Se-BSSHL） and 68 simultaneous BSSHL （Si-BSSHL） were consecutively admitted between June 2008 and December 2015.Two sets of patients served as control groups：（1） USSHL patients with healthy contralateral ear and （2） USSHL patients with contralateral preexisting hearing loss （USSHLwCHL）.We retrospectively analyzed differences among four cohorts using analysis of variance,Kruskal-Wallis test,Welch＇s t-test,and Chi-square test as appropriate before and after propensity score matching （PSM） based on age,gender,and body mass index （BMI）.Results：The prevalence of idiopathic BSSHL was 8.6% （114/1329） among the total SSHL patients.In the total cohort,USSHL patients tended to be younger,female,and tended to have lower BMI,renal parameters,and total cholesterol in addition to higher high-density lipoprotein compared to the other three groups.Most routine blood indicators,some coagulation markers,and immunoglobulin M （H =13.4,P =0.004） were significantly different among the study groups.After PSM,the major significant differences were found in audiometric characteristics.Si-BSSHL and Se-BSSHL patients demonstrated similar hearing thresholds as USSHL but were significantly better than the USSHLwCHL patients across most frequencies before and after treatment （H =30.0,P 〈 0.001 for initial hearing and H =12.0,P =0.007 for final hearing）.Moreover,the BSSHL patients showed different hearing loss distribution patterns （more descending type,x2 =33.8,P =0.001） with less hearing gain （H =17.5,P 〈 0.001） compared to the USSHL patients.Conclusions：Idiopathic BSSHL is a relatively rare subtype of SSHL with a higher rate of descending audiogram type and inferior hearing outcome rather than being classified as a completely different disease entity compared to USSHL.

Thermoelectric transport properties of Pb-Sn-Te-Se system

IV-VI compounds are considered as promising thermoelectric materials, and high thermoelectric performance was achieved in IV-VI solid solutions. In this work, the thermoelectric properties of Pb-Sn-Te-Se-based solid solutions were systematically investigated. Among these solid solutions, it is found that a figure of merit （ZT） peak value of 1.0 at 873 K can be obtained in （PbTe）0.5（SnTe）o.5, on account of the combination of superior electrical properties in SnTe and low thermal conductivity in PbTe. Furthermore, we investigated and summarized the thermoelectric transport properties and proposed the thermoelectric performance maps for the IV- VI solid solutions in Pb-Sn-Te-Se system. This comprehensive investigation on Pb-Sn-Te-Se-based solid solutions can effectively guide and scan thermoelectric performance for a given unknown composition and enhance the thermoelectric properties in IV-VI compounds.

Realizing high thermoelectric properties in p-type polycrystalline SnSe by inducing DOS distortion

SnSe crystals have been discovered as one of the most efficient thermoelectric materials due to their remarkable thermal and electrical transports. But the polycrystalline SnSe possesses much lower performance especially for the low carrier mobility and electrical conductivity. We firstly attempted to explain and verify the difference in the electrical conductivity as a function of temperature between p-type crystalline and polycrystalline SnSe by considering the grain boundary effects in the polycrystalline samples. On the basis of 2% Na doping to optimize the carrier concentration, the carrier mobility is improved by further introducing In, leading to enhanced carrier mobility from 3 to 9 cm2·V^(-1)·s^(-1) in polycrystalline SnSe. Moreover, In doping introduces extra resonant levels in SnSe, which increases the density of states near Fermi level and leads to an enhanced band effective mass. Large Seebeck coefficient of ~205 l V·K^(-1) at 300 K and maximum power factor of ~7.5 l W·cm^(-1)·K^(-2) at 773 K can be obtained in the Sn_(0.975)Na_(0.02)In_(0.005) Se sample,leading to a competitively high dimensionless figure of merit(ZT) value exceeding 1.1 at 773 K.

Homologous layered InFeO3(ZnO)m:new promising abradable seal coating materials

As promising abradable seal coating materials used in high temperature range, the homologous layered InFeO3（ZnO）m （m = 1, 2, 3...20） have attracted great attention. In this short review, we summary the research progress in InFeO3（ZnO）m that were developed in our group. We first introduced a series of conventional abradable seal coating materials as a research motivation. Second, the phase composition and crystal structures of lnFeO3（ZnO）m system were presented. Then, their thermophysical properties, as the most important part, were introduced in detail. At last, the mechanical properties such as hardness, friction coefficient, erosion wear resistance of InFeO3（ZnO）m system were also described. Our summary indicates that InFeO3（ZnO）m sys- tems are promising abradable seal coating materials.

Estimation of the potential performance in p-type SnSe crystals through evaluating weighted mobility and effective mass

It has been proved that the thermoelectric performance of p-type SnSe crystals can be optimized through enhancing carrier concentration.The calculations of electronic band structure elucidate that this approach can be interpreted by including multiple valence bands.To better estimate the potential performance,we proposed the transport properties for p-type SnSe crystals and analyzed the weighted mobility from the experimental results.The weighted mobility approaches~600 cm^(2)V1s1 when the carrier concentration is as high as~6.31019 cm3.Combined with obtained lattice thermal conductivity,through rising carrier concentration,the quality factor B possesses significant improvements of~235%and 138%at 300 K and 773 K,respectively.Through comparing weighted mobility and Hall mobility,two effective mass values~0.9 me and 1.8 me can be derived using carrier concentrations.It is expected that the ZT~1.0 at 300K and ZT~2.9 at 773 K can be obtained when the carrier concentration of~8.01019 cm3 and the effective mass~1.8 me were selected.This work provides an alternative way to comprehend the performance optimization in thermoelectric community.

High thermoelectric figure of merit ZT>1 in SnS polycrystals

Eco-friendly tin sulfide(SnS)has attracted increasing attention in the thermoelectric community because of its elemental abundance and analogous crystal structure to SnSe as a new thermoelectric material.However,so far no high dimensionless thermoelectric figure of merit ZT>1 was reported in SnS polycrystals.This work found an effective strategy for enhancing the thermoelectric performance of ptype polycrystalline SnS by Ag doping and vacancy engineering,leading to three orders of magnitude increase in carrier concentration and optimized effective mass and carrier mobility.As a result of the enhanced electrical conductivity,three times higher power factor ~3.85 μW/cm K^(2) at 877 K is realized in Sn_(0.995)Ag_(0.005)S sample.Interestingly,nanostructuring with Ag nano-precipitates were formed in the Agdoped SnS sample.Moreover,with introducing Sn vacancies in the crystal structure of Sn_(0.995-vac)Ag_(0.005)S,the power factor further enhanced to~4.25 μW/cm K^(2).In addition to the low-frequency phonons scattering by Ag nano-precipitates,dislocations strengthens the scattering of mid-frequency phonon,leading to an ultralow lattice thermal conductivity <0.5 W/m K above 800 K and a record high ZT up to 1.1 at 877 K in Sn_(0.99)Ag_(0.005)S polycrystals.

Highly Textured N-Type SnSe Polycrystals with Enhanced Thermoelectric Performance

Thermoelectric materials,which directly convert heat into electricity based on the Seebeck effects,have long been investigated for use in semiconductor refrigeration or waste heat recovery.Among them,SnSe has attracted significant attention due to its promising performance in both p-type and n-type crystals;in particular,a higher out-of-plane ZT value could be achieved in ntype SnSe due to its 3D charge and 2D phonon transports.In this work,the thermoelectric transport properties of n-type polycrystalline SnSe were investigated with an emphasis on the out-of-plane transport through producing textural microstructure.The textures were fabricated using mechanical alloying and repeated spark plasma sintering(SPS),as a kind of hot pressing,aimed at producing strong anisotropic transports in n-type polycrystalline SnSe as that in crystalline SnSe.Results show that the lowest thermal conductivity of 0.36 Wm^(-1) K^(-1) was obtained at 783 K in perpendicular to texture direction.Interestingly,the electrical transport properties are less anisotropic and even nearly isotropic,and the power factors reach 681.3μWm^(-1) K^(-2) at 783 K along both parallel and perpendicular directions.The combination of large isotropic power factor and low anisotropic thermal conductivity leads to a maximum ZT of 1.5 at 783 K.The high performance elucidates the outstanding electrical and thermal transport behaviors in n-type polycrystalline SnSe,and a higher thermoelectric performance can be expected with future optimizing texture in n-type polycrystalline SnSe.

Investigation on halogen-doped n-type SnTe thermoelectrics

Recent theoretical predictions and experimental findings on the transport properties of n-type SnTe have triggered extensive researches on this simple binary compound,despite the realization of n-type SnTe being a great challenge.Herein,Cl as a donor dopant can effectively regulate the position of Fermi level in Sn_(0.6)Pb_(0.4)Te matrix and successfully achieve the n-type transport behavior in SnTe.An outstanding power factor of~14.7μW·cm^(-1)·K^(-2) at 300 K was obtained for Cl-doped Sn_(0.6)Pb_(0.4)Te sample.By combining the experimental analysis with theoretical calculations,the transport properties of n-type SnTe thermoelectrics doped with different halogen dopants(Cl,Br,and I)were then systematically investigated and estimated.The results demonstrated that Br and I had better doping efficiencies compared with Cl,which contributed to the well-optimized carrier concentrations of~1.03×10^(19)and~1.11×10^(19)cm^(-3)at 300 K,respectively.The improved n-type carrier concentrations effectively lead to the significant enhancement on the thermoelectric performance of n-type SnTe.Our study further promoted the experimental progress and deep interpretation of the transport features in n-type SnTe thermoelectrics.The present results could also be crucial for the development of n-type counterparts for SnTe-based thermoelectric devices.

Realizing ranged performance in SnTe through integrating bands convergence and DOS distortion

As a typical IV-VI compound,SnTe has aroused widely attentions in the thermoelectric community due its similar crystal and band structures with PbTe.However,both the large number of inherent Sn vacancies and high thermal conductivity result in inferior thermoelectric performance in intrinsic SnTe over a broad temperature.In this work,we successfully improved those disadvantages of SnTe via stepwisely Pb heavily alloying and then In doping.A significantly wide fraction of Pb into SnTe(0-50%)achieves multiple effects:(a)the carrier concentration of SnTe is reduced through decreasing Sn vacancies via alloying high solution Pb atoms in the matrix;(b)the band structure is optimized through promoting the convergence of the two valence bands,simultaneously enhancing the Seebeck coefficient;(c)HAADF-STEM coupled with EDS results illustrate that guest Pb atoms randomly and uniformly occupied Sn atomic sites in the matrix,concurrently strengthening the phonon scattering.Furthermore,we introduced indium into Sn_(0.6)Pb_(0.4)Te system to create resonant states further enlarging the power factors at low-medium temperature.The integration of bands convergence and DOS distortion achieves a considerably high ZT_(ave) of~0.67 over the wide temperature range of 300-823 K in(Sn_(0.6)Pb_(0.4))_(0.995)In_(0.005)Te sample.

Enhanced thermoelectric performance in Cl-doped BiSbSe_(3) with optimal carrier concentration and effective mass

Possessing inherently low thermal conductivity,BiSbSe_(3) is a promising thermoelectric material for medium temperature.Therefore,to substantially optimize the thermoelectric performance of BiSbSe_(3),researchers mainly focus on the strategies to improve its electrical transport properties.Among these strongly coupled thermoelectric parameters,carrier concentration and effective mass are two intrinsic variables to decisively affect the electrical transport properties.In this work,Cl as a donor dopant is effective to provide extra electrons in n-type BiSbSe_(3),and the carrier concentration and effective mass can be well optimized simultaneously with increasing Cl content owing to the multiple conduction bands in BiSbSe_(3).What’s more,maximum weighted mobility~53 cm^(2)V^(-1)s^(-1)is obtained in Cl-doped BiSbSe_(3),which contributes to a largely enhanced power factor~4.8μW cm^(-1)K^(-2)at room temperature and outperforms other halogen-doped BiSbSe_(3) samples.Finally,combining the significantly enhanced power factor and maintained low thermal conductivity,a maximum ZT~1.0 is achieved in Cl-doped BiSbSe_(3) at 800 K.

Highly-anisotropic optical and electrical properties in layered SnSe

Anisotropic materials are of considerable interest because of their unique combination of polarization- or direction-dependent electrical, optical, and thermoelectric properties. Low-symmetry two-dimensional （2D） materials formed by van der Waals stacking of covalently bonded atomic layers are inherently anisotropic. Layered SnSe exhibits a low degree of lattice symmetry, with a distorted NaC1 structure and an in-plane anisotropy. Here we report a systematic study of the in-plane anisotropic properties in layered SnSe, using angle-resolved Raman scattering, optical absorption, and electrical transport studies. The optical and electrical characterization was direction-dependent, and successfully identified the crystalline orientation in the layered SnSe. Furthermore, the dependence of Raman-intensity anisotropy on the SnSe flake thickness and the excitation wavelength were investigated by both experiments and theoretical calculations. Finally, the electrical transport studies demonstrated that few-layer SnSe field- effect transistors （FETs） have a large anisotropic ratio of carrier mobility （N 5.8） bet- ween the armchair and zigzag directions, which is a record high value reported for 2D anisotropic materials. The highly-anisotropic properties of layered SnSe indicate considerable promise for anisotropic optics, electronics, and optoelectronics.

Enhancing the thermoelectric performance of Bi2S3: A promising earth-abundant thermoelectric material

Recently, bismuth sulfide (Bi2S3) has attracted much attention in the thermoelectric community owing to its abundance, low cost, and advanced properties. However, its poor electrical transport properties have prevented Bi2S3 devices from realizing high thermoelectric performance. In this work, our motivation is to decrease the large electrical resistivity, which is recognized as the origin of the low ZT value in undoped Bi2S3. We combined melting and spark plasma sintering (SPS) in a continuous fabrication process to produce Bi2S3–xSex (x = 0, 0.09, 0.15, 0.21) and Bi2S2.85–ySe0.15Cly (y = 0.0015, 0.0045, 0.0075, 0.015, 0.03) samples. Our results show that Se alloying at S sites can narrow the band gap and activate intrinsic electron conduction, leading to a high power factor of ~2.0 μW·cm–1·K–2 at room temperature in Bi2S2.85S0.15, about 100 times higher than that of undoped Bi2S3. Moreover, our further introduction of Cl atoms into the S sites resulted in a second-stage optimization of carrier concentration and simultaneously reduced the lattice thermal conductivity, which contributed to a high ZT value of ~0.6 at 723 K for Bi2S2.835Se0.15Cl0.015. Our results indicate that high thermoelectric performance could be realized in Bi2S3 with earth-abundant and low-cost elements.

Slowing down the heat in thermoelectrics

Heat transport has various applications in solid materials.In particular,the thermoelectric technology provides an alternative approach to traditional methods for waste heat recovery and solid-state refrigeration by enabling direct and reversible conversion between heat and electricity.For enhancing the thermoelectric performance of the materials,attempts must be made to slow down the heat transport by minimizing their thermal conductivity(κ).In this study,a continuously developing heat transport model is reviewed first.Theoretical models for predicting the lattice thermal conductivity(κlat)of materials are summarized,which are significant for the rapid screening of thermoelectric materials with lowκlat.Moreover,typical strategies,including the introduction of extrinsic phonon scattering centers with multidimensions and internal physical mechanisms of materials with intrinsically lowκlat,for slowing down the heat transport are outlined.Extrinsic defect centers with multidimensions substantially scatter various-frequency phonons;the intrinsically lowκlat in materials with various crystal structures can be attributed to the strong anharmonicity resulting from weak chemical bonding,resonant bonding,low-lying optical modes,liquid-like sublattices,off-center atoms,and complex crystal structures.This review provides an overall understanding of heat transport in thermoelectric materials and proposes effective approaches for slowing down the heat transport to depressκlat for the enhancement of thermoelectric performance.

A sound velocity method for determining isobaric specific heat capacity

Isobaric specific heat capacity(Cp)is an important parameter not only in physics but also for most materials.Its accurate measurement is particularly critical for performance evaluation of thermoelectric materials,but the experiments by differential scanning calorimetry(DSC)often lead to large uncertainties in the measurements,especially at elevated temperatures.In this study,we propose a simple method to determine Cp by measuring the sound velocity(υ)based on lattice vibration and expansion theory.The relative standard error of theυis smaller than 1%,showing good accuracy and repeatability.The calculated Cp at elevated temperature(>300 K)increases slightly with increasing temperature due to the lattice expansion,which is more reasonable than the Dulong–Petit value.