Impact of Oxygen Stoichiometry on the Thermoelectric Properties of Bi2Sr2Co2Oy Thin Films.

In this study, we present a comprehensive analysis of the thermoelectric (TE) properties of highly c-axis-oriented thin films of layered misfit cobaltates Bi2Sr2Co2Oy. The films exhibit a high c-axis orientation, facilitating precise measurements of electronic transport and TE properties along the a-b crystallographic plane. Our findings reveal that the presence of nearly stoichiometric oxygen content results in high thermopower with metallic conductivity, while the annealing of the films in a reduced oxygen atmosphere eliminates their metallic behavior. According to the well-established Heike's limit, the thermopower tends to become temperature independent when the thermal energy significantly exceeds the bandwidth, which provides a rough estimation of charge carrier density by using the Heike's formula. This observation suggests that the dominant contribution to the thermopower comes from the narrow Co-t2g bands near the Fermi energy. Our study demonstrates that the calculated thermopower value using Heike's formula, based on the Hall electron density of the Bi2Sr2Co2Oy thin films at 300 K, aligns well with the experimental results, shedding light on the intriguing TE properties of this family of layered cobaltate oxide films.

Enhanced Thermal Conductivity of Free-Standing Double-Walled Carbon Nanotube Networks.

Nanomaterials are driving advances in technology due to their oftentimes superior properties over bulk materials. In particular, their thermal properties become increasingly important as efficient heat dissipation is required to realize high-performance electronic devices, reduce energy consumption, and prevent thermal damage. One application where nanomaterials can play a crucial role is extreme ultraviolet (EUV) lithography, where pellicles that protect the photomask from particle contamination have to be transparent to EUV light, mechanically strong, and thermally conductive in order to withstand the heat associated with high-power EUV radiation. Free-standing carbon nanotube (CNT) films have emerged as candidates due to their high EUV transparency and ability to withstand heat. However, the thermal transport properties of these films are not well understood beyond bulk emissivity measurements. Here, we measure the thermal conductivity of free-standing CNT films using all-optical Raman thermometry at temperatures between 300 and 700 K. We find thermal conductivities up to 50 W m-1 K-1 for films composed of double-walled CNTs, which rises to 257 W m-1 K-1 when considering the CNT network alone. These values are remarkably high for randomly oriented CNT networks, roughly seven times that of single-walled CNT films. The enhanced thermal conduction is due to the additional wall, which likely gives rise to additional heat-carrying phonon modes and provides a certain resilience to defects. Our results demonstrate that free-standing double-walled CNT films efficiently dissipate heat, enhancing our understanding of these promising films and how they are suited to applications in EUV lithography.

Functionalizing Dendrimers for Targeted Delivery of Bioactive Molecules to Macrophages: A Potential Treatment for Mycobacterium tuberculosis Infection-A Review.

Tuberculosis (TB) is an infectious disease caused by Mycobacterium tuberculosis that replicates inside human alveolar macrophages. This disease causes significant morbidity and mortality throughout the world. According to the World Health Organization 1.4 million people died of this disease in 2021. This indicates that despite the progress of modern medicine, improvements in diagnostics, and the development of drug susceptibility tests, TB remains a global threat to public health. In this sense, host-directed therapy may provide a new approach to the cure of TB, and the expression of miRNAs has been correlated with a change in the concentration of various inflammatory mediators whose concentrations are responsible for the pathophysiology of M. tuberculosis infection. Thus, the administration of miRNAs may help to modulate the immune response of organisms. However, direct administration of miRNAs, without adequate encapsulation, exposes nucleic acids to the activity of cytosolic nucleases, limiting their application. Dendrimers are a family of highly branched molecules with a well-defined architecture and a branched conformation which gives rise to cavities that facilitate physical immobilization, and functional groups that allow chemical interaction with molecules of interest. Additionally, dendrimers can be easily functionalized to target different cells, macrophages among them. In this sense, various studies have proposed the use of different cell receptors as target molecules to aim dendrimers at macrophages and thus release drugs or nucleic acids in the cell of interest. Based on the considerations, the primary objective of this review is to comprehensively explore the potential of functionalized dendrimers as delivery vectors for miRNAs and other therapeutic agents into macrophages. This work aims to provide insights into the use of functionalized dendrimers as an innovative approach for TB treatment, focusing on their ability to target and deliver therapeutic cargo to macrophages.

Engineering Heat Transport Across Epitaxial Lattice-Mismatched van der Waals Heterointerfaces.

Artificially engineered 2D materials offer unique physical properties for thermal management, surpassing naturally occurring materials. Here, using van der Waals epitaxy, we demonstrate the ability to engineer extremely insulating thermal metamaterials based on atomically thin lattice-mismatched Bi2Se3/MoSe2 superlattices and graphene/PdSe2 heterostructures with exceptional thermal resistances (70-202 m2 K/GW) and ultralow cross-plane thermal conductivities (0.012-0.07 W/mK) at room temperature, comparable to those of amorphous materials. Experimental data obtained using frequency-domain thermoreflectance and low-frequency Raman spectroscopy, supported by tight-binding phonon calculations, reveal the impact of lattice mismatch, phonon-interface scattering, size effects, temperature, and interface thermal resistance on cross-plane heat dissipation, uncovering different thermal transport regimes and the dominant role of long-wavelength phonons. Our findings provide essential insights into emerging synthesis and thermal characterization methods and valuable guidance for the development of large-area heteroepitaxial van der Waals films of dissimilar materials with tailored thermal transport characteristics.

Enhanced Thermoelectric Properties of Misfit Bi2Sr2-xCaxCo2Oy: Isovalent Substitutions and Selective Phonon Scattering.

Layered Bi-misfit cobaltates, such as Bi2Sr2Co2Oy, are the natural superlattice of an electrically insulating rocksalt (RS) type Bi2Sr2O4 layer and electrically conducting CoO2 layer, stacked along the crystallographic c-axis. RS and CoO2 layers are related through charge compensation reactions (or charge transfer). Therefore, thermoelectric transport properties are affected when doping or substitution is carried out in the RS layer. In this work, we have shown improved thermoelectric properties of spark plasma sintered Bi2Sr2-xCaxCo2Oy alloys (x = 0, 0.3 and 0.5). The substitution of Ca atoms affects the thermal properties by introducing point-defect phonon scattering, while the electronic conductivity and thermopower remain unaltered.

Application of Synchrotron Radiation-Based Fourier-Transform Infrared Microspectroscopy for Thermal Imaging of Polymer Thin Films.

The thermal imaging of surfaces with microscale spatial resolution over micro-sized areas remains a challenging and time-consuming task. Surface thermal imaging is a very important characterization tool in mechanical engineering, microelectronics, chemical process engineering, optics, microfluidics, and biochemistry processing, among others. Within the realm of electronic circuits, this technique has significant potential for investigating hot spots, power densities, and monitoring heat distributions in complementary metal-oxide-semiconductor (CMOS) platforms. We present a new technique for remote non-invasive, contactless thermal field mapping using synchrotron radiation-based Fourier-transform infrared microspectroscopy. We demonstrate a spatial resolution better than 10 um over areas on the order of 12,000 um2 measured in a polymeric thin film on top of CaF2 substrates. Thermal images were obtained from infrared spectra of poly(methyl methacrylate) thin films heated with a wire. The temperature dependence of the collected infrared spectra was analyzed via linear regression and machine learning algorithms, namely random forest and k-nearest neighbor algorithms. This approach speeds up signal analysis and allows for the generation of hyperspectral temperature maps. The results here highlight the potential of infrared absorbance to serve as a remote method for the quantitative determination of heat distribution, thermal properties, and the existence of hot spots, with implications in CMOS technologies and other electronic devices.

Excitation and detection of acoustic phonons in nanoscale systems.

Phonons play a key role in the physical properties of materials, and have long been a topic of study in physics. While the effects of phonons had historically been considered to be a hindrance, modern research has shown that phonons can be exploited due to their ability to couple to other excitations and consequently affect the thermal, dielectric, and electronic properties of solid state systems, greatly motivating the engineering of phononic structures. Advances in nanofabrication have allowed for structuring and phonon confinement even down to the nanoscale, drastically changing material properties. Despite developments in fabricating such nanoscale devices, the proper manipulation and characterization of phonons continues to be challenging. However, a fundamental understanding of these processes could enable the realization of key applications in diverse fields such as topological phononics, information technologies, sensing, and quantum electrodynamics, especially when integrated with existing electronic and photonic devices. Here, we highlight seven of the available methods for the excitation and detection of acoustic phonons and vibrations in solid materials, as well as advantages, disadvantages, and additional considerations related to their application. We then provide perspectives towards open challenges in nanophononics and how the additional understanding granted by these techniques could serve to enable the next generation of phononic technological applications.

Spectroscopic and Thermal Characterization of Extra Virgin Olive Oil Adulterated with Edible Oils.

The substitution of extra virgin olive oil with other edible oils is the primary method for fraud in the olive-oil industry. Developing inexpensive analytical methods for confirming the quality and authenticity of olive oils is a major strategy towards combatting food fraud. Current methods used to detect such adulterations require complicated time- and resource-intensive preparation steps. In this work, a comparative study incorporating Raman and infrared spectroscopies, photoluminescence, and thermal-conductivity measurements of different sets of adulterated olive oils is presented. The potential of each characterization technique to detect traces of adulteration in extra virgin olive oils is evaluated. Concentrations of adulterant on the order of 5% can be detected in the Raman, infrared, and photoluminescence spectra. Small changes in thermal conductivity were also found for varying amounts of adulterants. While each of these techniques may individually be unable to identify impurity adulterants, the combination of these techniques together provides a holistic approach to validate the purity and authenticity of olive oils.

Unraveling Heat Transport and Dissipation in Suspended MoSe2 from Bulk to Monolayer.

Understanding heat flow in layered transition metal dichalcogenide (TMD) crystals is crucial for applications exploiting these materials. Despite significant efforts, several basic thermal transport properties of TMDs are currently not well understood, in particular how transport is affected by material thickness and the material's environment. This combined experimental-theoretical study establishes a unifying physical picture of the intrinsic lattice thermal conductivity of the representative TMD MoSe2 . Thermal conductivity measurements using Raman thermometry on a large set of clean, crystalline, suspended crystals with systematically varied thickness are combined with ab initio simulations with phonons at finite temperature. The results show that phonon dispersions and lifetimes change strongly with thickness, yet the thinnest TMD films exhibit an in-plane thermal conductivity that is only marginally smaller than that of bulk crystals. This is the result of compensating phonon contributions, in particular heat-carrying modes around ≈0.1 THz in (sub)nanometer thin films, with a surprisingly long mean free path of several micrometers. This behavior arises directly from the layered nature of the material. Furthermore, out-of-plane heat dissipation to air molecules is remarkably efficient, in particular for the thinnest crystals, increasing the apparent thermal conductivity of monolayer MoSe2 by an order of magnitude. These results are crucial for the design of (flexible) TMD-based (opto-)electronic applications.

On the thermoelectric properties of Nb-doped SrTiO3 epitaxial thin films.

The exploration for thermoelectric thin films of complex oxides such as SrTiO3-based oxides is driven by the need for miniaturized harvesting devices for powering the Internet of Things (IoT). However, there is still not a clear consensus in the literature for the underlying influence of film thickness on thermoelectric properties. Here, we report the fabrication of epitaxial thin films of 6% Nb-doped SrTiO3 on (001) (LaAlO3)0.3(Sr2AlTaO6)0.7 (LSAT) single crystal using pulsed laser deposition (PLD) where the film thickness was varied from 2 nm to 68 nm. The thickness dependence shows a subtle increase of tetragonality of the thin film lattice and a gradual drop of the electrical conductivity, the density of charge carriers, and the thermoelectric Seebeck coefficient as the film thickness decreases. DFT-based calculations show that ∼2.8% increase in tetragonality results in an increased splitting between t2g and eg orbitals to ∼42.3 meV. However, experimentally observed tetragonality for films between 68 to 13 nm is only 0.06%. Hence, the effect of thickness on tetragonality is neglected. We have discussed the decrease of conductivity and the Seebeck coefficient based on the decrease of carriers and change in the scattering mechanism, respectively.

Review on Sol-Gel Synthesis of Perovskite and Oxide Nanomaterials.

Sol-Gel is a low cost, well-established and flexible synthetic route to produce a wide range of micro- and nanostructures. Small variations in pH, temperature, precursors, time, pressure, atmosphere, among others, can lead to a wide family of compounds that share the same molecular structures. In this work, we present a general review of the synthesis of LaMnO3, SrTiO3, BaTiO3 perovskites and zinc vanadium oxides nanostructures based on Sol-Gel method. We discuss how small changes in the parameters of the synthesis can modify the morphology, shape, size, homogeneity, aggregation, among others, of the products. We also discuss the different precursors, solvents, working temperature, reaction times used throughout the synthesis. In the last section, we present novel uses of Sol-Gel with organic materials with emphasis on carbon-based compounds. All with a perspective to improve the method for future applications in different technological fields.

Anisotropic Thermal Conductivity of Crystalline Layered SnSe2.

The degree of thermal anisotropy affects critically key device-relevant properties of layered two-dimensional materials. Here, we systematically study the in-plane and cross-plane thermal conductivity of crystalline SnSe2 films of varying thickness (16-190 nm) and uncover a thickness-independent thermal conductivity anisotropy ratio of about ∼8.4. Experimental data obtained using Raman thermometry and frequency domain thermoreflectance showed that the in-plane and cross-plane thermal conductivities monotonically decrease by a factor of 2.5 with decreasing film thickness compared to the bulk values. Moreover, we find that the temperature-dependence of the in-plane component gradually decreases as the film becomes thinner, and in the range from 300 to 473 K it drops by more than a factor of 2. Using the mean free path reconstruction method, we found that phonons with MFP ranging from ∼1 to 53 and from 1 to 30 nm contribute to 50% of the total in-plane and cross-plane thermal conductivity, respectively.

Reversing the Humidity Response of MoS2- and WS2-Based Sensors Using Transition-Metal Salts.

Two-dimensional materials, such as transition-metal dichalcogenides (TMDs), are attractive candidates for sensing applications due to their high surface-to-volume ratio, chemically active edges, and good electrical properties. However, their electrical response to humidity is still under debate and experimental reports remain inconclusive. For instance, in different studies, the impedance of MoS2-based sensors has been found to either decrease or increase with increasing humidity, compromising the use of MoS2 for humidity sensing. In this work, we focus on understanding the interaction between water and TMDs. We fabricated and studied humidity sensors based on MoS2 and WS2 coated with copper chloride and silver nitrate. The devices exhibited high chemical stability and excellent humidity sensing performance in relative humidity between 4 and 80%, with response and recovery times of 2 and 40 s, respectively. We have systematically investigated the humidity response of the materials as a function of the type and amount of induced metal salt and observed the reverse action of sensing mechanisms. This phenomenon is explained based on a detailed structural analysis of the samples considering the Grotthuss mechanism in the presence of charge trapping, which was represented by an appropriate lumped-element model. Our findings open up a possibility to tune the electrical response in a facile manner and without compromising the high performance of the sensor. They offer an insight into the time-dependent performance and aging of the TMD-based sensing devices.

Understanding the Molecular Basis of 5-HT4 Receptor Partial Agonists through 3D-QSAR Studies.

Alzheimer's disease (AD) is a neurodegenerative disorder whose prevalence has an incidence in senior citizens. Unfortunately, current pharmacotherapy only offers symptom relief for patients with side effects such as bradycardia, nausea, and vomiting. Therefore, there is a present need to provide other therapeutic alternatives for treatments for these disorders. The 5-HT4 receptor is an attractive therapeutic target since it has a potential role in central and peripheral nervous system disorders such as AD, irritable bowel syndrome, and gastroparesis. Quantitative structure-activity relationship analysis of a series of 62 active compounds in the 5-HT4 receptor was carried out in the present work. The structure-activity relationship was estimated using three-dimensional quantitative structure-activity relationship (3D-QSAR) techniques based on these structures' field molecular (force and Gaussian field). The best force-field QSAR models achieve a value for the coefficient of determination of the training set of R2training = 0.821, and for the test set R2test = 0.667, while for Gaussian-field QSAR the training and the test were R2training = 0.898 and R2test = 0.695, respectively. The obtained results were validated using a coefficient of correlation of the leave-one-out cross-validation of Q2LOO = 0.804 and Q2LOO = 0.886 for force- and Gaussian-field QSAR, respectively. Based on these results, novel 5-HT4 partial agonists with potential biological activity (pEC50 8.209-9.417 for force-field QSAR and 9.111-9.856 for Gaussian-field QSAR) were designed. In addition, for the new analogues, their absorption, distribution, metabolism, excretion, and toxicity properties were also analyzed. The results show that these new derivatives also have reasonable pharmacokinetics and drug-like properties. Our findings suggest novel routes for the design and development of new 5-HT4 partial agonists.

Heat Transport Control and Thermal Characterization of Low-Dimensional Materials: A Review.

Heat dissipation and thermal management are central challenges in various areas of science and technology and are critical issues for the majority of nanoelectronic devices. In this review, we focus on experimental advances in thermal characterization and phonon engineering that have drastically increased the understanding of heat transport and demonstrated efficient ways to control heat propagation in nanomaterials. We summarize the latest device-relevant methodologies of phonon engineering in semiconductor nanostructures and 2D materials, including graphene and transition metal dichalcogenides. Then, we review recent advances in thermal characterization techniques, and discuss their main challenges and limitations.

Enhancement of Thermal Boundary Conductance of Metal-Polymer System.

In organic electronics, thermal management is a challenge, as most organic materials conduct heat poorly. As these devices become smaller, thermal transport is increasingly limited by organic-inorganic interfaces, for example that between a metal and a polymer. However, the mechanisms of heat transport at these interfaces are not well understood. In this work, we compare three types of metal-polymer interfaces. Polymethyl methacrylate (PMMA) films of different thicknesses (1-15 nm) were spin-coated on silicon substrates and covered with an 80 nm gold film either directly, or over an interface layer of 2 nm of an adhesion promoting metal-either titanium or nickel. We use the frequency-domain thermoreflectance (FDTR) technique to measure the effective thermal conductivity of the polymer film and then extract the metal-polymer thermal boundary conductance (TBC) with a thermal resistance circuit model. We found that the titanium layer increased the TBC by a factor of 2, from 59 × 106 W·m-2·K-1 to 115 × 106 W·m-2·K-1, while the nickel layer increased TBC to 139 × 106 W·m-2·K-1. These results shed light on possible strategies to improve heat transport in organic electronic systems.

Nanowire forest of pnictogen-chalcogenide alloys for thermoelectricity.

Pnictogen and chalcogenide compounds have been seen as high-potential materials for efficient thermoelectric conversion over the past few decades. It is also known that with nanostructuration, the physical properties of these pnictogen-chalcogenide compounds can be further enhanced towards a more efficient heat conversion. Here, we report the reduced thermal conductivity of a large ensemble of Bi2Te3 alloy nanowires (70 nm in diameter) with selenium for n-type and antimony for p-type (Bi2Te3-ySey and Bi2-xSbxTe3 respectively). The nanowire growth was carried out through electrodeposition in nanoporous aluminium oxide templates with high aspect ratios leading to a forest (109 per centimetre square) of nearly identical nanowires. The temperature dependence of thermal conductivity for the nanowire ensembles was acquired through a highly sensitive 3ω measurement technique. The change in the thermal conductivity of nanowires is largely affected by the roughness in addition to the size effect due to enhanced boundary scattering. The major factor that influences the thermal conductivity was found to be the ratio of the rms roughness to the correlation length of the nanowire. With a high Seebeck coefficient and electrical conductivity at room temperature, the overall thermoelectric figure of merit ZT allows the consideration of such forests of nanowires as efficient potential building blocks of future TE devices.

Modification of the Raman Spectra in Graphene-Based Nanofluids and Its Correlation with Thermal Properties.

It is well known that by dispersing nanoparticles in a fluid, the thermal conductivity of the resulting nanofluid tends to increase with the concentration of nanoparticles. However, it is not clear what the mechanism behind this phenomenon is. Raman spectroscopy is a characterization technique connecting the molecular and macroscopic world, and therefore, it can unravel the puzzling effect exerted by the nanomaterial on the fluid. In this work, we report on a comparative study on the thermal conductivity, vibrational spectra and viscosity of graphene nanofluids based on three different amides: N, N-dimethylacetamide (DMAc); N, N-dimethylformamide (DMF); and N-methyl-2-pyrrolidinone (NMP). A set of concentrations of highly stable surfactant-free graphene nanofluids developed in-house was prepared and characterized. A correlation between the modification of the vibrational spectra of the fluids and an increase in their thermal conductivity in the presence of graphene was confirmed. Furthermore, an explanation of the non-modification of the thermal conductivity in graphene-NMP nanofluids is given based on its structure and a peculiar arrangement of the fluid.

Impact of the Regularization Parameter in the Mean Free Path Reconstruction Method: Nanoscale Heat Transport and Beyond.

The understanding of the mean free path (MFP) distribution of the energy carriers in materials (e.g., electrons, phonons, magnons, etc.) provides a key physical insight into their transport properties. In this context, MFP spectroscopy has become an important tool to describe the contribution of carriers with different MFP to the total transport phenomenon. In this work, we revise the MFP reconstruction technique and present a study on the impact of the regularization parameter on the MFP distribution of the energy carriers. By using the L-curve criterion, we calculate the optimal mathematical value of the regularization parameter. The effect of the change from the optimal value in the MFP distribution is analyzed in three case studies of heat transport by phonons. These results demonstrate that the choice of the regularization parameter has a large impact on the physical information obtained from the reconstructed accumulation function, and thus cannot be chosen arbitrarily. The approach can be applied to various transport phenomena at the nanoscale involving carriers of different physical nature and behavior.