New Directions for Low‐Dimensional Thermoelectric Materials

Many of the recent advances in enhancing the thermoelectric figure of merit are linked to nanoscale phenomena found both in bulk samples containing nanoscale constituents and in nanoscale samples themselves. Prior theoretical and experimental proof‐of‐principle studies on quantum‐well superlattice and quantum‐wire samples have now evolved into studies on bulk samples containing nanostructured constituents prepared by chemical or physical approaches. In this Review, nanostructural composites are shown to exhibit nanostructures and properties that show promise for thermoelectric applications, thus bringing together low‐dimensional and bulk materials for thermoelectric applications. Particular emphasis is given in this Review to the ability to achieve 1) a simultaneous increase in the power factor and a decrease in the thermal conductivity in the same nanocomposite sample and for transport in the same direction and 2) lower values of the thermal conductivity in these nanocomposites as compared to alloy samples of the same chemical composition. The outlook for future research directions for nanocomposite thermoelectric materials is also discussed.     

Probing Anisotropic Thermal Conductivity of Transition Metal Dichalcogenides MX2 (M = Mo,W and X = S,Se) using Time‐Domain Thermoreflectance

Transition metal dichalcogenides (TMDs) are a group of layered 2D semiconductors that have shown many intriguing electrical and optical properties. However, the thermal transport properties in TMDs are not well understood due to the challenges in characterizing anisotropic thermal conductivity. Here, a variable‐spot‐size time‐domain thermoreflectance approach is developed to simultaneously measure both the in‐plane and the through‐plane thermal conductivity of four kinds of layered TMDs (MoS₂, WS₂, MoSe₂, and WSe₂) over a wide temperature range, 80–300 K. Interestingly, it is found that both the through‐plane thermal conductivity and the Al/TMD interface conductance depend on the modulation frequency of the pump beam for all these four compounds. The frequency‐dependent thermal properties are attributed to the nonequilibrium thermal resistance between the different groups of phonons in the substrate. A two‐channel thermal model is used to analyze the nonequilibrium phonon transport and to derive the intrinsic thermal conductivity at the thermal equilibrium limit. The measurements of the thermal conductivities of bulk TMDs serve as an important benchmark for understanding the thermal conductivity of single‐ and few‐layer TMDs.     

Noncovalent Functionalization of Pnictogen Surfaces: From Small Molecules to 2D Heterostructures

Beyond graphene, 2D pnictogen polymers are rapidly growing among the family of 2D materials. Due to their unique properties, this group has received considerable interest in recent years. Those properties include tunable electronic band gaps, high charge carrier mobility, and in‐plane anisotropic properties. This Review covers the noncovalent functionalization of pnictogen surfaces considering experimental and theoretical studies. Noncovalent functionalization is of great importance for effective modulation of the electronic structure of these materials as well as improvement of their stability toward surface oxidation. This Review highlights their noncovalent modification by organic molecules, in which enhanced surface stability of phosphorene and generated functionalized materials for applications in biomedical, supercapacitors, energy storage, and biosensors. Moreover, the noncovalent interactions with small molecules show its significance for sensing applications. Lastly, the interactions of pnictogen sheets with other 2D materials and their applications for van der Waals heterostructure formation are discussed. Current state‐of‐the‐art as well as future perspectives in this field are covered.     

Nanomembrane‐Based,Thermal‐Transport Biosensor for Living Cells

Knowledge of materials' thermal‐transport properties, conductivity and diffusivity, is crucial for several applications within areas of biology, material science and engineering. Specifically, a microsized, flexible, biologically integrated thermal transport sensor is beneficial to a plethora of applications, ranging across plants physiological ecology and thermal imaging and treatment of cancerous cells, to thermal dissipation in flexible semiconductors and thermoelectrics. Living cells pose extra challenges, due to their small volumes and irregular curvilinear shapes. Here a novel approach of simultaneously measuring thermal conductivity and diffusivity of different materials and its applicability to single cells is demonstrated. This technique is based on increasing phonon‐boundary‐scattering rate in nanomembranes, having extremely low flexural rigidities, to induce a considerable spectral dependence of the bandgap‐emission over excitation‐laser intensity. It is demonstrated that once in contact with organic or inorganic materials, the nanomembranes' emission spectrally shift based on the material's thermal diffusivity and conductivity. This NM‐based technique is further applied to differentiate between different types and subtypes of cancer cells, based on their thermal‐transport properties. It is anticipated that this novel technique to enable an efficient single‐cell thermal targeting, allow better modeling of cellular thermal distribution and enable novel diagnostic techniques based on variations of single‐cell thermal‐transport properties.     

Layer‐Tunable Phosphorene Modulated by the Cation Insertion Rate as a Sodium‐Storage Anode

Liquid phase exfoliation of few‐layer phosphorene (FL‐P) is extensively explored in recent years. Nevertheless, their deficiencies such as ultralong sonication time, limited flake size distribution, and uncontrollable thicknesses are major hurdles for the development of phosphorene‐based materials. Herein, electrochemical cationic intercalation has been introduced to prepare phosphorene, through which large‐area FL‐P without surface functional groups can be efficiently attained (less than 1 h). More importantly, its layer number (from 2 to 11 layers) can be manipulated by changing the applied potential. The as‐obtained phosphorene delivers superior sodium‐storage performances when directly utilized as an anode material in sodium‐ion batteries. This electrochemical cation insertion method to prepare phosphorene should greatly facilitate the development of phosphorene‐based technologies. Moreover, this work provides the possibility for the scalable preparation of monolayer 2D materials by exploring intercalation ions. Additionally, the successful electrochemical exfoliation of phosphorene can promote the application of electrochemical exfoliation in other 2D materials.     

Phosphorene and Phosphorene‐Based Materials – Prospects for Future Applications

Phosphorene, a single‐ or few‐layered semiconductor material obtained from black phosphorus, has recently been introduced as a new member of the family of two‐dimensional (2D) layered materials. Since its discovery, phosphorene has attracted significant attention, and due to its unique properties, is a promising material for many applications including transistors, batteries and photovoltaics (PV). However, based on the current progress in phosphorene production, it is clear that a lot remains to be explored before this material can be used for these applications. After providing a comprehensive overview of recent advancements in phosphorene synthesis, advantages and challenges of the currently available methods for phosphorene production are discussed. An overview of the research progress in the use of phosphorene for a wide range of applications is presented, with a focus on enabling important roles that phosphorene would play in next‐generation PV cells. Roadmaps that have the potential to address some of the challenges in phosphorene research are examined because it is clear that the unprecedented chemical, physical and electronic properties of phosphorene and phosphorene‐based materials are suitable for various applications, including photovoltaics.     

二维黑磷物理性质及化学稳定性的研究进展

1914年科研工作者首次合成了黑磷的块体形式。在黑磷沉寂了100年之后,2014年人们成功地将其薄化到少层状态,得到了新型二维纳米材料——二维黑磷。它是由磷原子堆叠而成的单一元素的二维层状半导体材料,具有合适的可控直接带隙、高的载流子迁移率、高的漏电流调制率、较高的开关电流比、良好的导电导热能力和明显的平面各向异性等性质,在低维无机半导体领域备受关注。二维黑磷是一种具有众多优异性质的内禀p型材料,但在空气中的不稳定性使得目前还不能分离得到大面积磷烯(即单原子层黑磷)薄膜,这限制了二维黑磷的应用。本文综述了自2014年以来国内外关于二维黑磷的研究进展,系统介绍了二维黑磷的结构、制备与性质,重点归纳了包括电学性质、光学性质、力学性质、热学性质和磁学性质在内的物理性质及化学稳定性。最后总结并展望了二维黑磷作为电子材料的广阔前景。     

An effective thermal conductivity model of nanofluids with a cubical arrangement of spherical particles

The theoretical investigation of the effective thermal conductivities of nanofluids, a new class of solid-liquid suspensions, is important in both predicting and designing nanofluids with effective thermal conductivities. We have developed a new thermal conductivity model for nanofluids that is based on the assumption that monosized spherical particles are uniformly dispersed in the liquid and are located at the vertexes of a simple cubic lattice, with each particle surrounded by a liquid layer having a thermal conductivity that differs from that of the bulk liquid. This model nanofluid with a cubical arrangement of nanoparticles gives a more practical upper limit of thermal conduction than a model nanofluid with a parallel arrangement of nanoparticles. The new model unexpectedly shows a nonlinear relationship of thermal conductivity with particle concentration, whereas the conductivity-concentration curve changes from convex upward to concave upward with increasing volume concentration. The effects of particle and layer parameters on the effective thermal conductivities are also analyzed. A comparison of predicted thermal conductivity values and experimental data shows that the predicted values are much higher than the experimental data, a finding that indicates that there is a potential to further improve the effective thermal conductivities of nanofluids with more uniformly dispersed particles.     

Defect Engineering in Few‐Layer Phosphorene

Defect engineering in 2D phosphorene samples is becoming an important and powerful technique to alter their properties, enabling new optoelectronic applications, particularly at the infrared wavelength region. Defect engineering in a few‐layer phosphorene sample via introduction of substrate trapping centers is realized. In a three‐layer (3L) phosphorene sample, a strong photoluminescence (PL) emission peak from localized excitons at ≈1430 nm is observed, a much lower energy level than free excitonic emissions. An activation energy of ≈77 meV for the localized excitons is determined in temperature‐dependent PL measurements. The relatively high activation energy supports the strong stability of the localized excitons even at elevated temperature. The quantum efficiency of localized exciton emission in 3L phosphorene is measured to be approximately three times higher than that of free excitons. These results could enable exciting applications in infrared optoelectronics.     

Soft Multifunctional Composites and Emulsions with Liquid Metals

Binary mixtures of liquid metal (LM) or low‐melting‐point alloy (LMPA) in an elastomeric or fluidic carrier medium can exhibit unique combinations of electrical, thermal, and mechanical properties. This emerging class of soft multifunctional composites have potential applications in wearable computing, bio‐inspired robotics, and shape‐programmable architectures. The dispersion phase can range from dilute droplets to connected networks that support electrical conductivity. In contrast to deterministically patterned LM microfluidics, LMPA‐ and LM‐embedded elastomer (LMEE) composites are statistically homogenous and exhibit effective bulk properties. Eutectic Ga‐In (EGaIn) and Ga‐In‐Sn (Galinstan) alloys are typically used due to their high conductivity, low viscosity, negligible nontoxicity, and ability to wet to nonmetallic materials. Because they are liquid‐phase, these alloys can alter the electrical and thermal properties of the composite while preserving the mechanics of the surrounding medium. For composites with LMPA inclusions (e.g., Field's metal, Pb‐based solder), mechanical rigidity can be actively tuned with external heating or electrical activation. This progress report, reviews recent experimental and theoretical studies of this emerging class of soft material architectures and identifies current technical challenges and opportunities for further advancement.     

Thin-Film Thermal-Conductivity Measurement on Semi-Conducting Polymer Material Using the 3ω Technique

Organic solar cells have gained increasing interest in recent years due to their promising low-cost processing possibility and high throughput compared to inorganic solar cells. Since the efficiency of organic solar cells is still low, further optimization has to be done. Reliable simulation of solar cell layout and performance strongly depends on correct input data of the electrical and thermal transport properties of the applied film materials. In many cases these material properties are only available for bulk material if available at all. Owing to the given film thicknesses on the order of tenths to hundreds of nanometer and to the preparation methods, the properties of the used system can differ from the bulk material values. For determination of the thin-film thermal conductivity, only a few measurement methods are known to provide accurate results with one of them being the 3ω technique. It allows the determination of the thermal conductivity of bulk materials as well as thin films down to a thickness of around 50 nm. This study is part of an investigation on the influence of local hot spots, generated by defects in the active layer of organic solar cells, and on the charge carrier mobility as well as the propagation of the hot spot due to the thermal conduction of the material. Applying the 3ω technique, the effective thermal conductivity of solution-derived poly(3-hexylthiophene) thin films of different thickness on a common glass substrate was investigated.     

Simultaneous Measurement of Thermal Conductivity and Specific Heat in a Single TDTR Experiment

Time-domain thermoreflectance (TDTR) technique is a powerful thermal property measurement method, especially for nano-structures and material interfaces. Thermal properties can be obtained by fitting TDTR experimental data with a proper thermal transport model. In a single TDTR experiment, thermal properties with different sensitivity trends can be extracted simultaneously. However, thermal conductivity and volumetric heat capacity usually have similar trends in sensitivity for most materials; it is difficult to measure them simultaneously. In this work, we present a two-step data fitting method to measure the thermal conductivity and volumetric heat capacity simultaneously from a set of TDTR experimental data at single modulation frequency. This method takes full advantage of the information carried by both amplitude and phase signals; it is a more convenient and effective solution compared with the frequency-domain thermoreflectance method. The relative error is lower than 5 % for most cases. A silicon wafer sample was measured by TDTR method to verify the two-step fitting method.     

模拟聚乙烯块体相变和导热的粗粒化模型和势场建立EI北大核心CSCD

建立适用于介观尺度聚乙烯块体相变和导热分子模拟的粗粒化模型及势场,并对其进行验证。基于全原子分子动力学模拟结果,采用多态-迭代玻尔兹曼变换法进行粗粒化分子动力学模拟来获得粗粒化势场。结果表明:粗粒化势场采用函数形式的势能描述,易于使用;对比全原子模拟结果,粗粒化势场能够较准确地模拟聚乙烯块体的静态结构性质;聚乙烯块体在300 K和500 K下密度的模拟值与实验值误差小于3%,玻璃化转变温度和熔化温度的模拟值与实验值相符较好;单链聚乙烯导热系数的粗粒化势场模拟值与全原子模拟值较一致,无序聚乙烯块体导热系数的模拟值与实验值吻合较好。研究结果为介观尺度聚乙烯的导热研究提供了一种更高效的模拟方法。     

Conductivity Maximum in 3D Graphene Foams

In conventional foams, electrical properties often play a secondary role. However, this scenario becomes different for 3D graphene foams (GrFs). In fact, one of the motivations for synthesizing 3D GrFs is to inherit the remarkable electrical properties of individual graphene sheets. Despite immense experimental efforts to study and improve the electrical properties of 3D GrFs, lack of theoretical studies and understanding limits further progress. The causes to this embarrassing situation are identified as the multiple freedoms introduced by graphene sheets and multiscale nature of this problem. In this article, combined with transport modeling and coarse‐grained molecular dynamic (MD) simulations, a theoretical framework is established to systematically study the electrical conducting properties of 3D GrFs with or without deformation. In particular, through large‐scale and massive calculations, a general relation between contact area and conductance for two van der Waals bonded graphene sheets is demonstrated, in terms of which the conductivity maximum phenomenon in GrFs is first theoretically proposed and its competition mechanism is explained. Moreover, the theoretical prediction is consistent with previous experimental observations.     

2D V‐V Binary Materials: Status and Challenges

2D phosphorene, arsenene, antimonene, and bismuthene, as a fast‐growing family of 2D monoelemental materials, have attracted enormous interest in the scientific community owing to their intriguing structures and extraordinary electronic properties. Tuning the monoelemental crystals into bielemental ones between group‐VA elements is able to preserve their advantages of unique structures, modulate their properties, and further expand their multifunctional applications. Herein, a review of the historical work is provided for both theoretical predictions and experimental advances of 2D V‐V binary materials. Their various intriguing electronic properties are discussed, including band structure, carrier mobility, Rashba effect, and topological state. An emphasis is also given to their progress in fabricated approaches and potential applications. Finally, a detailed presentation on the opportunities and challenges in the future development of 2D V‐V binary materials is given.     

Scalable Synthesis of 2D Si Nanosheets

2D Si nanomaterials have attracted tremendous attention due to their novel properties and a wide range of potential applications from electronic devices to energy storage and conversion. However, high‐quality and large‐scale fabrication of 2D Si remains challenging. This study reports a room‐temperature and one‐step synthesis technique that leads to large‐scale and low‐cost production of Si nanosheets (SiNSs) with thickness ≈4 nm and lateral size of several micrometers, based on the intrinsic delithiation process of chemically leaching lithium from the Li₁₃Si₄ alloy. Together with experimental results, a combination of theoretical modeling and atomistic simulations indicates that the formation of single SiNS arises from spontaneous delamination of nanosheets from their substrate due to delithiation‐induced mismatch. Subsequently, the synthesized Si nanosheets evolve from amorphous to nanocrystalline to crystalline structures during annealing at different temperatures. It is demonstrated that these SiNSs possess unique mechanical properties, in particular ultralow friction, in contrast to their bulk counterparts.     

Recent Progress on Antimonene: A New Bidimensional Material

Antimonene, defined in sensu stricto as a single layer of antimony atoms, is recently the focus of numerous theoretical works predicting a variety of interesting properties and is quickly attracting the attention of the scientific community. However, what places antimonene in a different category from other 2D crystals is its strong spin–orbit coupling and a drastic evolution of its properties from the monolayer to the few‐layer system. The recent isolation of this novel 2D material pushes the interest for antimonene even further. Here, a review of both theoretical predictions and experimental results is compiled. First, an account of the calculations anticipating an electronic band structure suitable for optoelectronics and thermoelectric applications in monolayer form and a topological semimetal in few‐layer form is given. Second, the different approaches to produce antimonene—mechanical and liquid phase exfoliation, and epitaxial growth methods—are reviewed. In addition, this work also reports the main characterization techniques used to study this exotic material. This review provides insights for further exploring the appealing properties of antimonene and puts forward the opportunities and challenges for future applications from (opto)electronic device fabrication to biomedicine.     

Anisotropic thermal conductivity of Ge quantum-dot and symmetrically strained Si/Ge superlattices

We report the first experimental results on the temperature dependent in-plane and cross-plane thermal conductivities of a symmetrically strained Si/Ge superlattice and a Ge quantum-dot superlattice measured by the two-wire 3 omega method. The measured thermal conductivity values are highly anisotropic and are significantly reduced compared to the bulk thermal conductivity of the structures. The results can be explained by using heat transport models based on the Boltzmann transport equation with partially diffusive scattering of the phonons at the superlattice interfaces.     

Wetting‐Induced Climbing for Transferring Interfacially Assembled Large‐Area Ultrathin Pristine Graphene Film

Owing to inherent 2D structure, marvelous mechanical, electrical, and thermal properties, graphene has great potential as a macroscopic thin film for surface coating, composite, flexible electrode, and sensor. Nevertheless, the production of large‐area graphene‐based thin film from pristine graphene dispersion is severely impeded by its poor solution processability. In this study, a robust wetting‐induced climbing strategy is reported for transferring the interfacially assembled large‐area ultrathin pristine graphene film. This strategy can quickly convert solvent‐exfoliated pristine graphene dispersion into ultrathin graphene film on various substrates with different materials (glass, metal, plastics, and cloth), shapes (film, fiber, and bulk), and hydrophobic/hydrophilic patterns. It is also applicable to nanoparticles, nanofibers, and other exfoliated 2D nanomaterials for fabricating large‐area ultrathin films. Alternate climbing of different ultrathin nanomaterial films allows a layer‐by‐layer transfer, forming a well‐ordered layered composite film with the integration of multiple pristine nanomaterials at nanometer scale. This powerful strategy would greatly promote the development of solvent‐exfoliated pristine nanomaterials from dispersions to macroscopic thin film materials.     

Nanomechanical and Charge Transport Properties of Two‐Dimensional Atomic Sheets

The materials properties of graphene and other two‐dimensional atomic sheets are influenced by atomic‐scale defects, mechanical deformation, and microstructures. Thus, for graphene‐based applications, it is essential to uncover the roles of atomic‐scale defects and domain structures of two‐dimensional layers in charge transport properties. This review highlights recent studies of nanomechanical and charge transport properties of two‐dimensional atomic sheets, including graphene, MoS₂, and boron nitrides. Because of intrinsic structural differences, two‐dimensional atomic sheets give rise to unique nanomechanical properties, including a dependence on layer thickness and chemical modification that is in contrast to three‐dimensional continuum media. Mapping of local conductance and nanomechanical properties on a graphene layer can be used to image the domain and microstructures of two‐dimensional atomic layers. This paper also reviews recent experimental and theoretical findings on the role of bending, defects, and microstructures on nanomechanical and transport properties of graphene‐derived materials.