The thermoelectric properties of nanostructured silicon are not fully understood despite their initial promise. While the anomalously low thermal conductivity has attracted much work, the impact of nanostructuring on the power factor has mostly escaped attention. While initial reports did not find any significant changes to the power factor compared to the bulk, subsequent detailed measurements on p-type silicon nanowires showed a stark reduction in the Seebeck coefficient when compared to similarly doped bulk. The reduction is consistent with the disappearance of the phonon drag contribution, due to phonon boundary scattering. Here, we report measurements on a different nanostructure, holey silicon films, to test if similar loss of phonon drag can be observed. By devising experiments where all properties are measured on the same sample, we show that though these films possess electrical conductivity close to that in the bulk at comparable doping, they exhibit considerably smaller thermopower. The data are consistent with loss of phonon drag. At neck distances between 120 - 230 nm, the power factor at optimal doping is $\sim$ 50 percent that of the bulk. These insights are useful in the practical design of future thermoelectric devices based on nanostructured silicon.
In this study, we use the transient thermal grating optical technique \textemdash a non-contact, laser-based thermal metrology technique with intrinsically high accuracy \textemdash to investigate room-temperature phonon-mediated thermal transport in two nanoporous holey silicon membranes with limiting dimensions of 100 nm and 250 nm respectively. We compare the experimental results to ab initio calculations of phonon-mediated thermal transport according to the phonon Boltzmann transport equation (BTE) using two different computational techniques. We find that the calculations conducted within…
Thermoelectric devices convert temperature gradients into electrical power and vice versa, thus enabling energy scavenging from waste heat, sensing and cooling. Yet, many of these attractive applications are hindered by the limited efficiency of thermoelectric materials, especially in the low temperature regime. This review provides a summary of the recent advances in the design of new efficient silicon--based thermoelectric materials through nanostructuring, alloying and chemical optimization, emphasizing the contribution from theory and atomistic modeling.
Single-crystalline silicon is well known to be a poor thermoelectric material due to its high thermal conductivity. Most excellent research has focused on ways to decrease its thermal conductivity while retaining acceptably large power factors (PFs). Less effort has been spent to enhance the PF in poly and nanocrystalline silicon, instead. Here we show that in boron-hyperdoped nanocrystalline thin films PF may be increased up to 33 mW K$^{-2}$m$^{-1}$ at 300 K when hydrogen embedded in the film during deposition is removed. The result makes nanocrystalline Si a realistic competitor of Bi$_2$Te…
Thermoelectric device is a promising next-generation energy solution owing to its capability to transform waste heat into useful electric energy, which can be realized in materials with high elec- tric conductivities and low thermal conductivities. A recently synthesized silicon allotrope of Si$_{24}$ features highly anisotropic crystal structure with nanometre-sized regular pores. Here, based on first-principles study without any empirical parameter, we show that the slightly doped Si$_{24}$ can pro- vide an order-of-magnitude enhanced thermoelectric figure of merit at room temperature, compa…
Ion beam irradiation has recently emerged as a versatile approach to functional materials design. We show in this work that patterned defective regions generated by ion beam irradiation of silicon can create a phonon glass electron crystal (PGEC), a longstanding goal of thermoelectrics. By controlling the effective diameter of and spacing between the defective regions, molecular dynamics simulations suggest a reduction of the thermal conductivity by a factor of $\approx$20 is achievable. Boltzmann theory shows that the thermoelectric power factor remains largely intact in the damaged material.…
Enhancement of the electronic thermoelectric properties of bulk strained silicon-germanium alloys using the scattering relaxation times from first principles
Lack of materials which are thermoelectrically efficient and economically attractive is a challenge in thermoelectricity. Silicon could be a good thermoelectric material offering CMOS compatibility, harmlessness and cost reduction but it features a too high thermal conductivity. High harvested power density of 7W/cm2 at deltaT=30K is modeled based on a thin-film lateral architecture of thermo-converter that takes advantage of confinement effects to reduce the thermal conductivity. The simulation leads to the conclusion that 10nm thick Silicon has 10 times higher efficiency than bulk.
Herein, we report the use of nanostructured crystalline Si as a thermoelectric material and its integration into thermoelectric harvesters. The proof-of-concept relies on the partial suppression of lattice thermal transport by introducing pores with dimensions scaling between the electron mean free path and the phonon mean free path. In other words, we artificially aimed at the electron crystal phonon glass tradeoff targeted for thermoelectric efficiency. The devices were fabricated using CMOS compatible processes and exhibited power generation from a few microWatts per cm^2 to a few milliWatt…
Silicon carbide nanoparticles with diameters around 8 nm and with narrow size distribution have been finely mixed with doped silicon nanopowders and sintered into bulk samples to investigate the influence of nanoinclusions on electrical and thermal transport properties. We have compared the thermoelectric properties of samples ranging from 0-5% volume fraction of silicon carbide. The silicon carbide nanoinclusions lead to a significant improvement in the thermoelectric figure of merit, ZT, largely due to an enhancement of the Seebeck coefficient. A semiclassical Boltzmann transport equation is…
We have combined the Boltzmann transport equation with an {\it ab initio} approach to compute the thermoelectric coefficients of semiconductors. Electron-phonon, ionized impurity, and electron-plasmon scattering rates have been taken into account. The electronic band structure and average intervalley deformation potentials for the electron-phonon coupling are obtained from the density functional theory. The linearized Boltzmann equation has then been solved numerically beyond the relaxation time approximation. Our approach has been applied to crystalline silicon. We present results for the mob…
Holey graphyne (HGY) is a recently synthesized two-dimensional semiconducting allotrope of carbon composed of a regular pattern of six and eight-vertex carbon rings. In this study, based on first-principles density functional theory and molecular dynamics simulations, we predict a similar stable porous boron nitride holey graphyne-like structure that we call BN-holey-graphyne (BN-HGY). The dynamical and thermal stability of the structure at room temperature is confirmed by performing calculations of the phonon dispersion relations, and also ab-initio molecular dynamics simulations. BN-HGY stru…
We present ultra-thin silicon membrane thermocouple bolometers suitable for fast and sensitive detection of low levels of thermal power and infrared radiation at room temperature. The devices are based on 40 nm-thick strain tuned single crystalline silicon membranes shaped into heater/absorber area and narrow n- and p-doped beams, which operate as the thermocouple. The electro-thermal characterization of the devices reveal noise equivalent power of 13 pW/rtHz and thermal time constant of 2.5 ms. The high sensitivity of the devices is due to the high Seebeck coefficient of 0.39 mV/K and reducti…
Introducing hierarchical disorder from multiple defects into materials through nanostructuring is one of the most promising directions to achieve extremely low thermal conductivities and thus improve thermoelectric performance. The success of nanostructuring relies on charge carriers having shorter mean-free-paths than phonons so that the latter can be selectively scattered. Nevertheless, introducing disorder into a material often comes at the expense of scattering charge carriers as well as phonons. In order to determine the tradeoff between the degradation of the lattice thermal conductivity…
The superposition of flexoelectronic doping and topological phonons give rise to topological electronic magnetism of phonon in an inhomogeneously strained Si in the bilayer structure with metal. In case of ferromagnetic metal and Si bilayer structure, the flexoelectronic doping will also give rise to larger spin current, which will lead to large spin to charge conversion due to topological electronic magnetism of phonon. By applying a temperature difference to ferromagnetic metal/Si bilayer structure under an applied strain gradient, a large thermoelectric response can be generated. In this ex…
We have investigated the optoelectronic and thermoelectric properties of hexagonal antiperovskites Ba$_3$DN (D = Sb, Bi) using DFT calculations. The calculated equilibrium lattice parameters of both compounds are in good agreement with the available data. The calculated electronic structures indicate that they are direct bandgap semiconductors and the values of bandgaps are 1.35 and 1.33 eV for Ba3SbN and Ba3BiN, respectively. The inclusion of the spin-orbit effect split the conduction bands and the band gap of Ba$_3$BiN is much reduced. These two compounds have a high absorption coefficient, …
We report here metal to insulator transition, colossal Seebeck coefficient and ultralow thermal conductivity (0.0057th of its bulk value, significantly smaller than many well-known thermoelectric materials and silicon, showing potential applications in thermoelectrics, electronics and photonics for heat dissipation) in monodispersed well characterized Ni nanoparticles. As a consequence, thermoelectric power factor and figure of merit are significantly enhanced compared to their bulk counterpart. Interestingly, a systematic crossover from metallic to semiconducting to finally electrically insul…
Significant reduction of lattice thermal conductivity by electron-phonon interaction in silicon with high carrier concentrations: a first-principles study
Interstitial defects are inevitably present in doped semiconductors that enable modern-day electronic, optoelectronic or thermoelectric technologies. Understanding of stability of interstitials and their bonding mechanisms in the silicon lattice was accomplished only recently with the advent of first-principles modeling techniques, supported by powerful experimental methods. However, much less attention has been paid to the effect of different naturally occurring interstitials on the thermal and electrical properties of silicon. In this work, we present a systematic study of the variability of…
In this work, both thermal and electrical transport properties of diamond$-$cubic Si (Si$-$I) and metastable R8 phase of Si (Si$-$XII) are comparatively studied by using first$-$principles calculations combined with Boltzmann transport theory. The metastable Si$-$XII shows one magnitude lower lattice thermal conductivity than stable Si$-$I from 300 to 500~K, attributed from the stronger phonon scattering in three$-$phonon scattering processes of Si$-$XII. For the electronic transport properties, although Si$-$XII with smaller band gap (0.22 eV) shows lower Seebeck coefficient, the electrical c…
Silicon is one of the most frequently used chemical elements of the periodic table in nanotechnology. Two-dimensional (2D) silicene, a silicon analog of graphene, has been readily obtained to make field-effect transistors since 2015. Recently, as new members of the silicene family, penta-silicene and its nanoribbon have been experimentally grown on Ag(110) surface with exotic electronic properties. However, the thermoelectric performance of penta-silicene has not been so far studied that would hinder its potential applications of electric generation from waste heat and solid-state Peltier cool…
In nanostructures phonon transport behaviour is distinctly different to transport in bulk materials such that materials with ultra low thermal conductivities and enhanced thermoelectric performance can be realized. Low thermal conductivities have been achieved in nanocrystalline materials that include hierarchical sizes of inclusions and pores. Nanoporous structures present a promising set of material properties and structures which allow for ultra-low thermal conductivity, even below the amorphous limit. In this paper we outline a semiclassical Monte Carlo code for the study of phonon transpo…
Si nanocrystals have been extensively studied because of their novel properties and their potential applications in electronic, optoelectronic, photovoltaic, thermoelectric and biological devices. These new properties are achieved through the combination of the quantum confinement of carriers and the strong influence of surface chemistry. As in the case of bulk Si the tuning of the electronic, optical and transport properties is related to the possibility of doping, in a controlled way, the nanocrystals. This is a big challenge since several studies have revealed that doping in Si nanocrystals…
Semiconductor superlattices have been extensively investigated for thermoelectric applications, to explore the effects of compositions, interface structures, and lattice strain environments on the reduction of thermal conductivity, and improvement of efficiency. Most studies assumed that their electronic properties remain unaffected compared to their bulk counterparts. However, recent studies demonstrated that electronic properties of silicon (Si)/germanium (Ge) superlattices show significant variations depending on compositions and growth substrates. These studies used a constant relaxation t…
In silicon, lattice thermal conductivity plays an important role in a wide range of applications such as thermoelectric and microelectronic devices. Grain boundaries (GBs) in polycrystalline silicon can significantly reduce lattice thermal conductivity, but the impact of GB atomic structures on it remains to be elucidated. This study demonstrates accurate predictions of the GB structures, GB energies, and GB phonon properties in silicon using machine learning potentials (MLPs). The results indicate that the MLPs enable robust GB structure searches owing to the fact that the MLPs were developed…
Since the emergence of monolayer graphene as a promising two-dimensional material, many other monolayer and few-layer materials have been investigated extensively. An experimental study of few-layer Si2Te3 was recently reported, showing that the material has diverse properties for potential applications in Si-based devices ranging from fully integrated thermoelectrics to optoelectronics to chemical sensors. This material has a unique layered structure: it has a hexagonal closed-packed Te sublattice, with Si dimers occupying octahedral intercalation sites. Here we report a theoretical study of …
