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Ca3Co4O9, a p-type thermoelectric material based on transition-metal oxides, has garnered significant interest due to its potential in thermoelectric applications. Its unique misfit-layered crystal structure contributes to low thermal conductivity and a high Seebeck coefficient, leading to a thermoelectric figure of merit (zT) of ≥1 at 1000 K. Conventionally, it has been believed that thermopower reaches its upper limit above 200 K. However, our thermopower measurements on polycrystalline Ca3Co4O9 samples have revealed an unexpected increase in thermopower above 380 K. In this study, we investigate the effects of high oxygen pressure annealing on Ca3Co4O9 and provide an explanation based on the mixed oxide states of cobalt and carrier hopping. Our results demonstrate that annealing induces modifications in the defect chemistry of Ca3Co4O9, leading to a decrease in electron hopping probability and the emergence of a thermal activation-like behavior in thermopower. These findings carry significant implications for the design and optimization of thermoelectric materials based on misfit cobaltates, opening new avenues for enhanced thermoelectric performance.

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.

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.

We report on the structural, mechanical, and thermal analysis of 40 nm thick polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) films coated with evaporated chromium layers of different thicknesses (1, 2, and 5 nm). Solvent annealing processes allow the structural control of the BCP films morphology by rearranging the position of the PEO cylinders parallel to the substrate plane. High-vacuum scanning thermal microscopy and ultrasonic force microscopy measurements performed in ambient pressure revealed that coated ultrathin metal layers strongly influence the heat dissipation in the BCP films and the local surface stiffness of the individual BCP domains, respectively. The measured tip-sample effective thermal resistance decreases from 6.1 × 107 to 2.5 × 107 K W-1 with increasing Cr film thickness. In addition, scanning probe microscopy measurements allow the thermal and mechanical mapping of the two segregated polymer domains (PEO-PS) of sub-50 nm characteristic sizes, with sub-10 nm thermal spatial resolution. The results revealed the effect of the surface morphology of the BCP and the incorporation of the metal film on the nanoscale thermal properties and volume self-assembly on the mechanical properties. The findings from this study provide insight into the formation of high aspect ratio BCP-metal structures with the more established applications in lithography. In addition, knowledge of the thermal and mechanical properties at the nanoscale is required in emergent applications, where BCPs, or polymers in general, are part of the structure or device. The performance of such devices is commonly related to the requirement of increased heat dissipation while maintaining mechanical flexibility.

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.

We present a comparative investigation of the influence of crystallinity and film thickness on the acoustic and thermal properties of layered PtSe films of varying thickness (1–40 layers) using frequency-domain thermo-reflectance, low-frequency Raman, and pump-probe coherent phonon spectroscopy. We find ballistic cross-plane heat transport up to ~30 layers PtSe and a 35% reduction in the cross-plane thermal conductivity of polycrystalline films with thickness larger than 20 layers compared to the crystalline films of the same thickness. First-principles calculations further reveal a high degree of thermal conductivity anisotropy and a remarkable large contribution of the optical phonons to the thermal conductivity in bulk (~20%) and thin PtSe films (~30%). Moreover, we show strong interlayer interactions in PtSe, short acoustic phonon lifetimes in the range of picoseconds, an out-of-plane elastic constant of 31.8 GPa, and a layer-dependent group velocity ranging from 1340 ms in bilayer to 1873 ms in eight layers of PtSe. The potential of tuning the lattice thermal conductivity of layered materials with the level of crystallinity and the real-time observation of coherent phonon dynamics open a new playground for research in 2D thermoelectric devices and provides guidelines for thermal management in 2D electronics.

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 MoSe. 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 MoSe by an order of magnitude. These results are crucial for the design of (flexible) TMD-based (opto-)electronic applications.

We report heat transport measurements on suspended single-layer graphene disks with radius of 150–1600 nm using a high-vacuum scanning thermal microscope. The results of this study revealed a radius-dependent thermal contact resistance between tip and graphene, with values between 1.15 and 1.52 × 108 KW−1. The observed scaling of thermal resistance with radius is interpreted in terms of ballistic phonon transport in suspended graphene discs with radius smaller than 775 nm. In larger suspended graphene discs (radius >775 nm), the thermal resistance increases with radius, which is attributed to in-plane heat transport being limited by phonon–phonon resistive scattering processes, which resulted in a transition from ballistic to diffusive thermal transport. In addition, by simultaneously mapping topography and steady-state heat flux signals between a self-heated scanning probe sensor and graphene with 17 nm thermal spatial resolution, we demonstrated that the surface quality of the suspended graphene and its connectivity with the Si/SiO2 substrate play a determining role in thermal transport. Our approach allows the investigation of heat transport in suspended graphene at sub-micrometre length scales and overcomes major limitations of conventional experimental methods usually caused by extrinsic thermal contact resistances, assumptions on the value of the graphene's optical absorbance and limited thermal spatial resolution.

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.

Many layered materials, such as graphene and transition metal dichalcogenides, can be exfoliated down to atomic or molecular monolayers. These materials exhibit exciting material properties that can be exploited for several promising device concepts. Thinner materials lead to an increased surface-to-volume ratio, with mono- and bi-layers being basically pure surfaces. Thin crystals containing more than two layers also often behave as an all-surface material, depending on the physical property of interest. As a result, flakes of layered materials are typically highly sensitive to their environment, which is undesirable for a broad range of studies and potential devices. Material systems based on suspended flakes overcome this issue, yet often require complex fabrication procedures. Here, we demonstrate the relatively straightforward fabrication of exfoliated MoSe flakes down to the monolayer, suspended over unprecedentedly large holes with a diameter of 15 µm. We describe our fabrication methods in detail, present characterization measurements of the fabricated structures, and, finally, exploit these suspended flakes for accurate optical absorption measurements.

Altres ajuts: the authors acknowledge the financial support from the CERCA Program (Generalitat de Catalunya )., We report on the structural, mechanical, and thermal analysis of 40 nm thick polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer (BCP) films coated with evaporated chromium layers of different thicknesses (1, 2, and 5 nm). Solvent annealing processes allow the structural control of the BCP films morphology by rearranging the position of the PEO cylinders parallel to the substrate plane. High-vacuum scanning thermal microscopy and ultrasonic force microscopy measurements performed in ambient pressure revealed that coated ultrathin metal layers strongly influence the heat dissipation in the BCP films and the local surface stiffness of the individual BCP domains, respectively. The measured tip-sample effective thermal resistance decreases from 6.1 × 107 to 2.5 × 107 K W-1 with increasing Cr film thickness. In addition, scanning probe microscopy measurements allow the thermal and mechanical mapping of the two segregated polymer domains (PEO-PS) of sub-50 nm characteristic sizes, with sub-10 nm thermal spatial resolution. The results revealed the effect of the surface morphology of the BCP and the incorporation of the metal film on the nanoscale thermal properties and volume self-assembly on the mechanical properties. The findings from this study provide insight into the formation of high aspect ratio BCP-metal structures with the more established applications in lithography. In addition, knowledge of the thermal and mechanical properties at the nanoscale is required in emergent applications, where BCPs, or polymers in general, are part of the structure or device. The performance of such devices is commonly related to the requirement of increased heat dissipation while maintaining mechanical flexibility.

This AIP article is published under license by AIP: https://publishing.aip.org/wp-content/uploads/2019/10/AIPP-Author-License.pdfPublishing.https://pubs.acs.org/page/policy/authorchoice_termsofuse.html, Altres ajuts: ICN2 is supported by the CERCA Programme/Generalitat de Catalunya., The widespread use of nanostructures and nanomaterials has opened up a whole new realm of challenges in thermal management, but also leads to possibilities for energy conversion, storage, and generation, in addition to numerous other technological applications. At the microscale and below, standard thermal measurement techniques reach their limits, and several novel methods have been developed to overcome these limitations. Among the most recent, contactless photothermal methods have been widely used and have proved their advantages in terms of versatility, temporal and spatial resolution, and even sensitivity in some situations. Among them, thermoreflectance and Raman thermometry have been used to measure the thermal properties from bulk materials to thin films, multilayers, suspended structures, and nanomaterials. This Tutorial presents the principles of these two techniques and some of their most common implementations. It expands to more advanced systems for spatial mapping and for probing of non-Fourier thermal transport. Finally, this paper concludes with discussing the limitations and perspectives of these techniques and future directions in nanoscale thermometry.

The widespread use of nanostructures and nanomaterials has opened up a whole new realm of challenges in thermal management, but also leads to possibilities for energy conversion, storage, and generation, in addition to numerous other technological applications. At the microscale and below, standard thermal measurement techniques reach their limits, and several novel methods have been developed to overcome these limitations. Among the most recent, contactless photothermal methods have been widely used and have proved their advantages in terms of versatility, temporal and spatial resolution, and even sensitivity in some situations. Among them, thermoreflectance and Raman thermometry have been used to measure the thermal properties from bulk materials to thin films, multilayers, suspended structures, and nanomaterials. This Tutorial presents the principles of these two techniques and some of their most common implementations. It expands to more advanced systems for spatial mapping and for probing of non-Fourier thermal transport. Finally, this paper concludes with discussing the limitations and perspectives of these techniques and future directions in nanoscale thermometry. I. INTRODUCTION

L'objectiu principal d'aquesta tesi és l'estudi de les propietats tèrmiques de materials nanoestructurats com un mitjà per controlar el transport de calor. Per a aquest propòsit s'han portat a terme mesures tèrmiques amb diferents tècniques experimentals a escales que cobreixen desenes de micròmetres fins a per sota de 50 nanòmetres. En aquest tesi s'estudien i es presenten dues tècniques experimentals en particular: (a) la microscòpia tèrmica d'escombrat (SThM) i (b) la termometria Raman amb dos làsers (2LRT). Aquestes tècniques s'han aplicat àmpliament per mesurar amb èxit propietats tèrmiques en diversos nanomaterials. En particular, s'investiguen dues configuracions del silici emprant 2LRT: (a) membranes de silici amb gruixos que van de 8 a 1000 nm i (b) membranes poroses periòdiques amb diferents paràmetres de xarxa i membranes amb patró desordenat. Els resultats obtinguts han mostrat que la conductivitat tèrmica en el pla de les membranes i la seva evolució en temperatura, des de la temperatura ambient a aproximadament 1000 K, es poden reduir i ajustar de manera eficaç per mitjà de (i) el gruix i (ii) el patró periòdic(forats). Atribuïm la reducció de la conductivitat tèrmica a l'escurçament del camí lliure dels fonons a causa de la dispersió difusa (incoherent) fonó en els límit de les superfícies. Hem demostrat a més que la dependència de la conductivitat tèrmica amb la temperatura en l'interval d'alta temperatura (400 a 1000 K) es regeix per fonons amb el camí lliure mitjà menor que 200 nm. Per investigar el transport tèrmic en nanoestructures suportades i a escala més petita, s'ha estudiat la transferència de calor entre sensors de sonda d'escombrat escalfats i els nanomaterials, com ara, (i) nanofils epitaxials en el pla d'aliatge Si1-xGex i (ii) nanoestructures basades en copolímer de blocs autoassemblats. En aquestes últimes estructures s'han aconseguit imatges tèrmiques d'alta resolució en estructures de mida per sota de 50 nm i amb resolució espacial, The main objective of this thesis is the study of thermal properties of nanostructured materials as a mean to control heat transport. For this purpose thermal measurements with different experimental techniques on length scales covering tens of microns to sub-50 have been performed. Two experimental techniques in particular have been studied and presented in this thesis: (a) the scanning thermal microscopy technique (SThM) and (b) the two-laser Raman thermometry (2LRT). These techniques have been extensively applied to successfully measure thermal properties in various nanomaterials. In particular, two configurations of Si based materials are investigated using 2LRT: (a) Si membranes with thicknesses ranging from to and (b) periodic porous membranes with different lattice parameters and disordered pattern. The results obtained showed that the in-plane thermal conductivity of silicon and its temperature evolution from room temperature to about 1000 can be effectively reduced and tuned by (i) thickness and (ii) periodic patterning (holes). We attribute the reduction of the thermal conductivity to the shortening of the phonon mean free path Λ due to diffuse (incoherent) phonon-boundary scattering. Furthermore, we showed that the temperature dependence of the thermal conductivity of Si membranes in the high temperature range from to is governed by phonons with mean free path smaller than 200 . To investigate thermal transport in supported nanostructures and in smaller length scale, we studied heat transfer between different heated scanning probe sensors and nanomaterials, such as, (i) in-plane epitaxial Si1-xGex alloy nanowires and (ii) self-assembled block copolymer nanostructures, provided high resolution thermal images of sub-50 structures with sub- spatial resolution. The combination of the two experimental techniques was crucial for the thermal characterization of different material systems and the better understanding of fundamental aspects of thermal transport.

Progress in the last few decades in nano-scale thermal transport has enabled a significant degree of control over heat and sound propagation by lattice vibrations - phonons. The latest investigations on the thermal properties of silicon, the most common material in electronics, micro- and nano-electro-mechanical systems (MEMS and NEMS) and photonics, have pointed to nanostructuring as a highly efficient approach to acoustic phonon engineering. Heat conduction in silicon can be effectively engineered by means of submicrometer porous thin free-standing membranes. Tunable thermal properties make these structures good candidates for integrated heat management units such as waste heat recovery, rectification or efficient heat dissipation. However, possible applications require detailed thermal characterization at high temperatures which, up to now, has been an experimental challenge. In this work we use the contactless two-laser Raman thermometry to study heat dissipation in periodic porous membranes at high temperatures via lattice conduction and air-mediated losses. We find the reduction of the thermal conductivity and its temperature dependence closely correlated with the structure feature size. Based on two-phonon Raman spectra, we attribute this behavior to diffuse (incoherent) phononboundary scattering. Furthermore, we investigate and quantify the heat dissipation via natural air-mediated cooling, which can be tuned by engineering the porosity.

Environmentally robust chemical sensors for monitoring industrial processes or infrastructures are lately becoming important devices in industry. Low complexity and wireless enabled characteristics can offer the required flexibility for sensor deployment in adaptable sensing networks for continuous monitoring and management of industrial assets. Here are presented the design, development and operation of a class of low cost photonic sensors for monitoring the ageing process and the operational characteristics of coolant fluids used in an industrial heavy machinery infrastructure. The chemical, physical and spectroscopic characteristics of specific industrial-grade coolant fluids were analyzed along their entire life cycle range, and proper parameters for their efficient monitoring were identified. Based on multimode polymer or silica optical fibers, wide range (3-11) pH sensors were developed by employing sol-gel derived pH sensitive coatings. The performances of the developed sensors were characterized and compared, towards their coolants' ageing monitoring capability, proving their efficiency in such a demanding application scenario and harsh industrial environment. The operating characteristics of this type of sensors allowed their integration in an autonomous wireless sensing node, thus enabling the future use of the demonstrated platform in wireless sensor networks for a variety of industrial and environmental monitoring applications.

The design and fabrication of phononic crystals (PnCs) hold the key to control the propagation of heat and sound at the nanoscale. However, there is a lack of experimental studies addressing the impact of order/disorder on the phononic properties of PnCs. Here, we present a comparative investigation of the influence of disorder on the hypersonic and thermal properties of two-dimensional PnCs. PnCs of ordered and disordered lattices are fabricated of circular holes with equal filling fractions in free-standing Si membranes. Ultrafast pump and probe spectroscopy (asynchronous optical sampling) and Raman thermometry based on a novel two-laser approach are used to study the phononic properties in the gigahertz (GHz) and terahertz (THz) regime, respectively. Finite element method simulations of the phonon dispersion relation and three-dimensional displacement fields furthermore enable the unique identification of the different hypersonic vibrations. The increase of surface roughness and the introduction of short-range disorder are shown to modify the phonon dispersion and phonon coherence in the hypersonic (GHz) range without affecting the room-temperature thermal conductivity. On the basis of these findings, we suggest a criteria for predicting phonon coherence as a function of roughness and disorder.

Heat conduction in 2D materials can be effectively engineered by means of controlling nanoscale grain structure. Afavorable thermal performance makes these structures excellent candidates for integrated heat management units. Here we show combined experimental and theoretical studies for MoS nanosheets in a nanoscale grain-size limit.Wereport thermal conductivity measurements on 5 nm thick polycrystalline MoS by means of 2-laser Raman thermometry. The free-standing, drum-like MoS nanomembranes were fabricated using a novel polymer- and residue-free, wet transfer, in which we took advantage of the difference in the surface energies between MoS and the growth substrate to transfer the CVD-grown nanosheets. The measurements revealed a strong reduction in the in-plane thermal conductivity down to about 0.73 ± 0.25 W m K. The results are discussed theoretically using finite elements method simulations for a polycrystalline film, and a scaling trend of the thermally conductivity with grain size is proposed.

A simple fiber optic based scheme for the selective detection of proteins, based on surface electrostatic interactions, is presented. The implementation of this method is conducted using a modified polymer optical fiber's surface and thin overlayers of properly designed sensitive copolymer materials with predesigned molecular characteristics. Block poly(styrene-b-2vinylpyridine) (PS-b-P2VP) and random PS-r-P2VP copolymers of the same monomers and similar molecular weights, were modified and used as sensing materials. This configuration proved to be efficient concerning the fast detection of charged proteins, and also the efficient discrimination of differently charged proteins such as lysozyme and bovine serum albumin. Results on the sensing performance of block and random copolymers are also discussed drawing conclusion on their efficiency given their considerable different fabrication cost.