硅功能化石墨烯热导率的分子动力学模拟

采用Tersoff势函数与Lennard-Jones势函数,结合速度形式的Verlet算法和Fourier定律,对单层和两层硅功能化石墨烯沿长度方向的导热性能进行了正向非平衡态分子动力学模拟.通过模拟发现,硅原子的加入改变了石墨烯声子的模式、平均自由程和移动速度,使得单层硅功能化石墨烯模型的热导率随着硅原子数目的增加而急剧地减小.在300 K至1000 K温度变化范围内,单层硅功能化石墨烯的热导率呈下降趋势,具有明显的温度效应.对双层硅功能化石墨烯而言,少量的硅原子嵌入,起到了提高热导率的作用,但当硅原子数目达到一定数量后,材料的导热性能下降.     

功能化单壁碳纳米管的热导率

采用基于BrennerⅡ势的非平衡态分子动力学方法，模拟研究了300K温度下经氢化学修饰的(10,0)单壁碳纳米管的热导率.研究显示功能化后碳管的热导率有明显减小，当有一列碳原子被氢化后（功能化程度为5%），碳管的热导率减小了大约1/3，为了进一步解释这种功能化对碳纳米管热导率的影响，计算了不同功能化程度下碳纳米管的声子谱.     

功能化单壁碳纳米管的热导率

采用基于BrennerⅡ势的非平衡态分子动力学方法,模拟研究了300K温度下经氢化学修饰的(10,0)单壁碳纳米管的热导率.研究显示功能化后碳管的热导率有明显减小,当有一列碳原子被氢化后（功能化程度为5%）,碳管的热导率减小了大约1/3,为了进一步解释这种功能化对碳纳米管热导率的影响,计算了不同功能化程度下碳纳米管的声子谱.     

How Does van der Waals Confinement Enhance Phonon Transport?

We study the mechanism of van der Waals(vdW)interactions on phonon transport in atomic scale,which would boost developments in heat management and energy conversion.Commonly,the vdW interactions are regarded as a hindrance in phonon transport.Here we propose that the vdW confinement can enhance phonon transport.Through molecular dynamics simulations,it is realized that the vdW confinement is able to make more than two-fold enhancement on thermal conductivity of both polyethylene single chain and graphene nanoribbon.The quantitative analyses of morphology,local vdW potential energy and dynamical properties are carried out to reveal the underlying physical mechanism.It is found that the confined vdW potential barriers reduce the atomic thermal displacement magnitudes,leading to less phonon scattering and facilitating thermal transport.Our study offers a new strategy to modulate the phonon transport.     

三氨基三硝基苯基高聚物粘结炸药热力学性质的理论计算研究

高聚物粘结炸药(PBX)的热力学性质是用于炸药结构响应、安全性评估、数值模拟分析等的重要参数.由于PBX结构的多尺度特性,完全采取实验方法精细表征这些参数存在巨大的挑战.本文运用第一性原理和分子动力学计算的方法,系统研究了三氨基三硝基苯(TATB)基高聚物粘结炸药的热力学参数和界面热传导性质.利用散射失配模型研究了TATB与聚偏二氟乙烯(PVDF)界面的热传导过程,发现热导率随温度升高而上升,并且在高温情况下接近于定值.基于分子动力学获得的TATB热导率并结合界面热导率,分析了PBX炸药的热导与颗粒尺寸的关系,当颗粒尺寸大于100 nm时,界面热阻对于PBX热导率的影响有限.     

Decomposition model for phonon thermal conductivity of a monatomic lattice

An analytical treatment of decomposition of the phonon thermal conductivity of a crystal with a monatomic unit cell is developed on the basis of a two-stage decay of the heat current autocorrelation function observed in molecular dynamics simulations. It is demonstrated that the contributions from the acoustic short- and long-range phonon modes to the total phonon thermal conductivity can be presented in the form of simple kinetic formulas, consisting of products of the heat capacity and the average relaxation time of the considered phonon modes as well as the square of the average phonon velocity. On the basis of molecular dynamics calculations of the heat current autocorrelation function, this treatment allows for a self-consistent numerical evaluation of the aforementioned variables. In addition, the presented analysis allows, within the Debye approximation, for the identification of the temperature range where classical molecular dynamics simulations can be employed for the prediction of phonon thermal transport properties. As a case example, Cu is considered.     

Phonon-mediated heat dissipation in a monatomic lattice: case study on Ni

The recently introduced analytical model for the heat current autocorrelation function of a crystal with a monatomic lattice [Evteev et al., Phil. Mag. 94 (2014) p. 731 and 94 (2014) p. 3992] is employed in conjunction with the Green–Kubo formalism to investigate in detail the results of an equilibrium molecular dynamics calculations of the temperature dependence of the lattice thermal conductivity and phonon dynamics in f.c.c. Ni. Only the contribution to the lattice thermal conductivity determined by the phonon–phonon scattering processes is considered, while the contribution due to phonon–electron scattering processes is intentionally ignored. Nonetheless, during comparison of our data with experiment an estimation of the second contribution is made. Furthermore, by comparing the results obtained for f.c.c. Ni model to those for other models of elemental crystals with the f.c.c. lattice, we give an estimation of the scaling relations of the lattice thermal conductivity with other lattice properties such as the coefficient of thermal expansion and the bulk modulus. Moreover, within the framework of linear response theory and the fluctuation-dissipation theorem, we extend our analysis in this paper into the frequency domain to predict the power spectra of equilibrium fluctuations associated with the phonon-mediated heat dissipation in a monatomic lattice. The practical importance of the analytical treatment lies in the fact that it has the potential to be used in the future to efficiently decode the generic information on the lattice thermal conductivity and phonon dynamics from a power spectrum of the acoustic excitations in a monatomic crystal measured by a spectroscopic technique in the frequency range of about 1–20 THz.     

Enhancement effect of asymmetry on the thermal conductivity of double-stranded chain systems

Using nonequilibrium molecular dynamics simulations, we study the thermal conductivity of asymmetric double chains. We couple two different single chains through interchain coupling to build three kinds of asymmetric double-stranded chain system: intrachain interaction, external potential, and mass asymmetric double chains. It is reported that asymmetry is helpful in improving the thermal conductivity of the system. We first propose double-heat flux channels to explain the influence of asymmetric structures on the thermal conductivity. The phonon spectral behaviour and finite size effect are also included.     

Two-fluid nature of phonon heat conduction in a monatomic lattice

The thermal resistance of a crystal lattice with a monatomic unit cell due to three-phonon scattering processes is investigated in detail theoretically. A general expression for the lattice thermal conductivity is derived from a combined analysis based on: (i) the Boltzmann equation and (ii) data on the heat current autocorrelation function obtained via molecular dynamics simulations in conjunction with the Green–Kubo formalism. It is argued that the phonon gas in a monatomic lattice conducts heat as if it consisted of two distinct parts (two ‘thermal fluids’), so that the lattice thermal conductivity can be decomposed into contributions from these two parts. The origin of the behaviour of the phonon gas, which is explored in the present work, is due to an intrinsic interplay between Umklapp and normal three-phonon scattering processes. New insight into the nature of the lattice thermal conductivity is demonstrated and the results of the present work are in agreement with previous studies in this area.     

Effect of isotope doping on phonon thermal conductivity of silicene nanoribbons: A molecular dynamics study

Silicene, a silicon analogue of graphene, has attracted increasing research attention in recent years because of its unique electrical and thermal conductivities. In this study, phonon thermal conductivity and its isotopic doping effect in silicene nanoribbons(SNRs) are investigated by using molecular dynamics simulations. The calculated thermal conductivities are approximately 32 W/mK and 35 W/mK for armchair-edged SNRs and zigzag-edged SNRs, respectively, which show anisotropic behaviors. Isotope doping induces mass disorder in the lattice, which results in increased phonon scattering, thus reducing the thermal conductivity. The phonon thermal conductivity of isotopic doped SNR is dependent on the concentration and arrangement pattern of dopants. A maximum reduction of about 15% is obtained at 50% randomly isotopic doping with ~(30)Si. In addition, ordered doping(i.e., isotope superlattice) leads to a much larger reduction in thermal conductivity than random doping for the same doping concentration. Particularly, the periodicity of the doping superlattice structure has a significant influence on the thermal conductivity of SNR. Phonon spectrum analysis is also used to qualitatively explain the mechanism of thermal conductivity change induced by isotopic doping. This study highlights the importance of isotopic doping in tuning the thermal properties of silicene, thus guiding defect engineering of the thermal properties of two-dimensional silicon materials.     

Layer and size dependence of thermal conductivity in multilayer graphene nanoribbons

Using nonequilibrium molecular dynamics method (NEMD), we have found that the thermal conductivity of multilayer graphene nanoribbons monotonously decreases with the increase of the number of layers which can be attributed to the phonon resonance effect of out-of-plane phonon modes. The reduction of thermal conductivity is proportional to the layer size, which is caused by the increase of phonon resonance. The results clearly show the dimensional evolution of thermal conductivity from quasi-one dimension to higher dimensions in graphene nanoribbons.     

固态金属中声子热传递的分子动力学模拟研究

固态金属中的热传递是声子和自由电子共同作用的结果。自由电子引起的热导率可以通过电导率,利用Wiedemann-Franz定律得到,声子引起的热导率目前仍然不能进行实验测量,只能借助其他方法来研究。本文采用非平衡分子动力学(NEMD)方法,用镶嵌原子方法(EAM)势能模型,模拟计算了不同厚度(1.760-10.56nm)金属镍薄膜中由于声子-声子作用引起的热导率。然后根据纳米厚度金属薄膜的热导率借助关联式推到宏观尺度下由于声子-声子作用引起的热导率。结果表明,对于纳米厚度金属薄膜,由于声子-声子作用引起的热导率比块体金属镍的热导率小一个数量级;薄膜厚度越小,声子-声子作用引起的热导率越小;对于块体金属镍,由于声子-声子作用引起的热导率约占其总热导率的33.0%左右。     

铝纳米颗粒的热物性及相变行为的分子动力学模拟

采用分子动力学方法模拟了纳米金属铝在粒径为0.8-3.2 nm 时的熔点、密度和声子热导率的变化, 研究了粒径为1.6 nm的铝纳米颗粒的密度、比热和声子热导率随温度的变化. 采用原子嵌入势较好地模拟了纳米金属铝的热物性及相变行为, 根据能量-温度曲线和比热容-温度曲线对铝纳米颗粒的相变温度进行了研究, 并利用表面能理论、尺寸效应理论对铝纳米颗粒熔点的变化进行了分析. 随着纳米粒径的不断增大, 铝纳米颗粒的熔点呈递增状态, 当粒径在2.2-3.2 nm时, 熔点的增幅减缓, 但仍处于递增趋势. 随着纳米粒径的增大, 铝纳米颗粒的密度呈单调递减, 热导率则呈线性单调递增, 且热导率的变化情况符合声子理论. 随着温度的升高, 粒径为1.6 nm的铝纳米颗粒的密度、热导率均减小. 该模拟从微观原子角度对纳米材料的热物性进行了研究, 对设计基于铝纳米颗粒的相变材料具有指导意义.     

Phonon relaxation and heat conduction in one-dimensional Fermiben Pastaben Ulam β lattices by molecular dynamics simulations

The phonon relaxation and heat conduction in one-dimensional Fermi-Pasta-Ulam (FPU) β lattices are studied by using molecular dynamics simulations. The phonon relaxation rate, which dominates the length dependence of the FPU β lattice, is first calculated from the energy autocorrelation function for different modes at various temperatures through equilibrium molecular dynamics simulations. We find that the relaxation rate as a function of wave number k is proportional to k^1.688, which leads to a N^0.41 divergence of the thermal conductivity in the framework of Green-Kubo relation. This is also in good agreement with the data obtained by non-equilibrium molecular dynamics simulations which estimate the length dependence exponent of the thermal conductivity as 0.415. Our results confirm the N^2/5 divergence in one-dimensional FPU β lattices. The effects of the heat flux on the thermal conductivity are also studied by imposing different temperature differences on the two ends of the lattices. We find that the thermal conductivity is insensitive to the heat flux under our simulation conditions. It implies that the linear response theory is applicable towards the heat conduction in one-dimensional FPU β lattices.     

Nanoscale thermal cloaking by in-situ annealing silicon membrane

With the advent of thermal metamaterials, many new thermal functionalities have been proposed, like thermal cloaking, concentrating, etc. However, these thermal functionalities are based on the transformation thermotics or scattering cancellation technique, which, derived from Fourier's law, cannot apply to the micro-/nanoscale counterparts. In this paper, we design a nanoscale thermal cloak based on a crystalline silicon (Si) membrane and investigate the in-plane phonon transport via non-equilibrium molecular dynamics (NEMD) simulation by in-situ tuning the thermal conductivity of the thermal cloak from crystalline Si to amorphous Si. The two-dimensional temperature profile is obtained, and the thermal cloaking effect is evaluated by the ratio of heat flux. By analyzing the phonon density of state (PDOS) and the mode participation ratio (MPR), the mechanism can be attributed to the phonon localization in the annealed cloaking region. The proposed nanoscale thermal cloak by in-situ tuned thermal conductivity, may trigger the development of nanoscale thermal functionalities and open avenues for and thermal management for nano-photonics and nano-electronics.     

Effects of fullerene coalescence on the thermal conductivity of carbon nanopeapods

The heat conduction and its dependence on fullerene coalescence in carbon nanopeapods (CNPs) have been investigated by equilibrium molecular dynamics simulations. The effects of fullerene coalescence on the thermal conductivity of CNPs were discussed under different temperatures. It is shown that the thermal conductivity of the CNPs decreases with the coalescence of encapsulated fullerene molecules. The thermal transmission mechanism of the effect of fullerene coalescence was analysed by the mass transfer contribution, the relative contributions of phonon oscillation frequencies to total heat current and the phonon vibrational density of states (VDOS). The mass transfer in CNPs is mainly attributed to the motion of encapsulated fullerene molecule and it gets more restricted with the coalescence of the fullerene. It shows that the low-frequency phonon modes below 20 THz contribute mostly to thermal conductivity in CNPs. The analysis of VDOS demonstrates that the dominating contribution to heat transfer is from the inner fullerene chain. With the coalescence of fullerene, the interfacial heat transfer between the CNT and fullerene chain is strengthened; however, the heat conduction of the fullerene chain decreases more rapidly at the same time.     

基于量子修正的石墨烯纳米带热导率分子动力学表征方法

本文提出了基于量子修正的非平衡态分子动力学模型,可用于石墨烯纳米带热导率的表征.利用该模型对不同温度下,不同手性及宽度的石墨烯纳米带热导率进行了研究,结果发现:相较于经典分子动力学模型给出的热导率随温度升高而单调下降的结论,在低于Debye温度的情况下,量子修正模型的计算结果出现了反常现象.本文研究还发现,石墨烯纳米带的热导率呈现出明显的边缘效应及尺度效应:锯齿型石墨烯纳米带的热导率明显高于扶手椅型石墨烯纳米带;全温段的热导率及热导率在低温段随温度变化的斜率均随宽度的增加而增大.最后,文章用Boltzmann声子散射理论对低温段的温度效应及尺度效应进行了阐释,其理论分析结果说明文章所建模型适合在全温段范围内对不同宽度和不同手性的热导率进行精确计算,可为石墨烯纳米带在传热散热领域的应用提供理论计算和分析依据.     

A comparison study on the electronic structures,lattice dynamics and thermoelectric properties of bulk silicon and silicon nanotubes

In order to investigate the mechanism of the electron and phonon transport in a silicon nanotube(SiNT),the electronic structures,the lattice dynamics,and the thermoelectric properties of bulk silicon(bulk Si)and a SiNT have been calculated in this work using density functional theory and Boltzmann transport theory.Our results suggest that the thermal conductivity of a SiNT is reduced by a factor of 1,while its electrical conductivity is improved significantly,although the Seebeck coefficient is increased slightly as compared to those of the bulk Si.As a consequence,the figure of merit(ZT)of a SiNT at 1200 K is enhanced by 12 times from 0.08 for bulk Si to 1.10.The large enhancement in electrical conductivity originates from the largely increased density of states at the Fermi energy level and the obviously narrowed band gap.The significant reduction in thermal conductivity is ascribed to the remarkably suppressed phonon thermal conductivity caused by a weakened covalent bonding,a decreased phonon density of states,a reduced phonon vibration frequency,as well as a shortened mean free path of phonons.The other factors influencing the thermoelectric properties have also been studied from the perspective of electronic structures and lattice dynamics.     

孔洞缺陷对二维石墨烯/氮化硼横向异质结热传导的调控

本文采用孔洞缺陷来实现对二维石墨烯/氮化硼横向异质结热导率的调控.平衡态分子动力学(EMD)计算结果表明,界面孔洞的引入会降低二维石墨烯/氮化硼横向异质结的热导率.相较于有序的孔洞分布,无序的孔洞分布能够更有效地降低异质结的热导率,这一现象可通过声子安德森局域化来解释.孔洞缺陷的存在导致声子的频率和波失发生变化,从而使声子散射变得更加频繁,孔洞随机分布时,则导致声子波在材料中发生多次反射和散射,最终形成局域振动模式.本研究揭示了孔洞缺陷降低二维石墨烯/氮化硼横向异质结热导率的物理机制,对二维热电材料的结构设计有一定的指导意义.     

单晶硅薄膜法向热导率分子动力学研究

采用非平衡分子动力学方法（NEMD）研究了平均温度为 500K、厚度为 2～32nm的单晶硅薄膜的法向热导率。模拟结果表明,薄膜热导率显著低于对应温度下的体硅单晶的实验值,并随膜厚度减小以接近线性的规律减小。用声子气动力论模型的分析结果与NEMD模拟相一致,表明纳米单晶硅薄膜中声子平均自由程显著减小。