Enhanced Photothermal Effect Assisted by Resonance Energy Transfer in Carbon/Covellite Core-Shell Nanoparticles toward a High-Performance Interfacial Water Evaporation Process.

Carbon and semiconductor nanoparticles are promising photothermal materials for various solar-driven applications. Inevitable recombination of photoinduced charge carriers in a single constituent, however, hinders the realization of a greater photothermal effect. Core-shell heterostructures utilizing the donor-acceptor pair concept with high-quality interfaces can inhibit energy loss from the radiation relaxation of excited species, thereby enhancing the photothermal effect. Here, core-shell structures composed of a covellite (CuS) shell (acceptor) and spherical carbon nanoparticle (CP) core (donor) (abbreviated as CP/CuS) are proposed to augment the photothermal conversion efficiency via the Förster resonance energy transfer (FRET) mechanism. The close proximity and spectral overlap of the donor and acceptor trigger the FRET mechanism, where the electronic excitation relaxation energy of the CP reinforces the plasmonic resonance and near-infrared absorption in CuS, resulting in boosting the overall photothermal conversion efficiency. CP/CuS core-shell coated on polyurethane (PU) foam exhibits a total solar absorption of 97.1%, leading to an elevation in surface temperature of 61.6 °C in dry conditions under simulated solar illumination at a power density of 1 kW m-2 (i.e., 1 sun). Leveraging the enhanced photothermal conversion emanated from the energy transfer effect in the core-shell structure, CP/CuS-coated PU foam achieves an evaporation rate of 1.62 kg m-2 h-1 and an energy efficiency of 93.8%. Thus, amplifying photothermal energy generation in core-shell structures via resonance energy transfer can be promising in solar energy-driven applications and thus merits further exploration.

Deposition of Ultrathin MgB2 Films from a Suspension Using Cosolvent Marangoni Flow.

Magnesium diboride (MgB2) has demonstrated, theoretically and experimentally, promise as a candidate material for hydrogen storage and has thus attracted much contemporary research interest. To study hydrogen gas adsorption on MgB2 thin films using a quartz crystal microbalance (QCM)─a workhorse apparatus for this specific experiment─MgB2 must be deposited uniformly on the active surface of the QCM without damaging the quartz's performance. In work presented here, a wet-chemistry colloid synthesis and deposition process of a MgB2 thin film on a gold (Au) surface was established to avoid the extreme conditions of conventional physical deposition methods. This process also counteracts the unwanted phenomena of drying droplets on a solid surface, particularly the coffee-ring effect. To verify the normal function of the QCM after MgB2 deposition and its ability to obtain meaningful data, simple gas adsorption tests were conducted on the QCM, and the MgB2 film on the QCM was characterized with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) for elemental analysis and surface roughness, respectively. To obtain information about the thickness and the involvement of the coffee-ring effect, the same synthesis route was applied on a similar gold substrate─an evaporated Au film on glass. XPS characterization of the film and its precursor suspension shows the potential existence of both MgB2 and its oxide forms. The film's thickness on evaporated Au was measured by scanning transmission electron microscopy (STEM) to be 3.9 nm. The resulting samples show mitigation of the coffee-ring effect through roughness measurements with AFM at two scan sizes of 50 × 50 and 1 × 1 µm2.

Enhancing the electrical properties of graphite nanoflake through gamma-ray irradiation.

Understanding changes in material properties through external stimuli is critical to validating the expected performance of materials as well as engineering material properties in a controlled manner. Here, we investigate a change in the c-axis electrical properties of graphite nanoflakes (GnFs) induced by gamma-ray irradiation, using conductive probe atomic force microscopy (CP-AFM). The fundamentals behind the change in their electrical properties are elucidated by analyzing the interlayer spacing, graphitization, and morphology. An increase in gamma-ray irradiation dose for GnFs leads to an exponential increase in the electrical conductance and a gradual decrease in the interlayer spacing, while accompanying indistinguishable changes in their morphology. Our experimental results suggest that the c-axis electrical conductance enhancement of GnFs with gamma-ray irradiation might be attributed to a reduction in interlayer spacing, though the created defects may also play a role. This study demonstrates that gamma-ray irradiation can be a promising route to tailor the electrical properties of GnFs.

Development of a rigid suspended micro-island device and robust measurement method for thermal transport measurements.

One of the most versatile techniques to study thermal transport in low dimensional materials utilizes a suspended micro-island device integrated with resistance thermometers. Advancements in experimental techniques with suspended micro-island devices resulted in increasing capabilities such as enhancing temperature resolution and expanding a measurable range of sample thermal conductance. In this work, we further improve the suspended micro-island based technique. Specifically, we present a rigid structure of the suspended micro-island device and robust measurement method for sequential heating. The rigid structure enabled by T-shaped beams prevents the displacement of suspended micro-islands, thus increasing the success rates of sample transfer especially for samples with a large cross-sectional area and short length. Besides, thermal isolation of micro-islands is maintained at a similar level through the T-shaped beams compared to conventional flat beams. Next, we introduce an advanced experimental approach that enables sequential heating to measure sample thermal conductance. Sequential heating in micro-islands can be used either to measure accurate sample thermal conductance even under unexpected asymmetric supporting beam configuration or to study thermal transport dependence on heat flow directions. Using a switch matrix for sequential heating eliminates the need for experimental reconfigurations during the experiment. We demonstrate the experimental method with thermal conductivity measurements of the Si nanowire under both the ideal symmetric beam configuration and replicated asymmetric beam configuration scenarios. The results show that the developed experimental method effectively eliminates potential experimental errors that can arise from the asymmetry in beam configurations.

Ion Write Microthermotics: Programing Thermal Metamaterials at the Microscale.

Considerable advances in manipulating heat flow in solids have been made through the innovation of artificial thermal structures such as thermal diodes, camouflages, and cloaks. Such thermal devices can be readily constructed only at the macroscale by mechanically assembling different materials with distinct values of thermal conductivity. Here, we extend these concepts to the microscale by demonstrating a monolithic material structure on which nearly arbitrary microscale thermal metamaterial patterns can be written and programmed. It is based on a single, suspended silicon membrane whose thermal conductivity is locally, continuously, and reversibly engineered over a wide range (between 2 and 65 W/m·K) and with fine spatial resolution (10-100 nm) by focused ion irradiation. Our thermal cloak demonstration shows how ion-write microthermotics can be used as a lithography-free platform to create thermal metamaterials that control heat flow at the microscale.

Thermoelectrics of Nanowires.

The field of thermoelectric research has undergone a renaissance and boom in the past two and a half decades, largely fueled by the prospect of engineering electronic and phononic properties in nanostructures, among which semiconductor nanowires (NWs) have served both as an important platform to investigate fundamental thermoelectric transport phenomena and as a promising route for high thermoelectric performance for diverse applications. In this Review, we provide a comprehensive look at various aspects of thermoelectrics of NWs. We start with a brief introduction of basic thermoelectric phenomena, followed by synthetic methods for thermoelectric NWs and a summary of their thermoelectric figures of merit (ZT). We then focus our discussion on charge and heat transport, which dictate thermoelectric power factor and thermal conductivity, respectively. For charge transport, we cover the basic principles governing the power factor and then review several strategies using NWs to enhance it, including earlier theoretical and experimental work on quantum confinement effects and semimetal-to-semiconductor transition, surface engineering and complex heterostructures to enhance the carrier mobility and power factor, and the recent emergence of topological insulator NWs. For phonon transport, we broadly categorize the work on thermal conductivity of NWs into five different effects: classic size effect, acoustic softening, surface roughness, complex NW morphology, and dimensional crossover. Finally, we discuss the integration of NWs for device applications for thermoelectric power generation and cooling. We conclude our review with some outlooks for future research.

Phase-transition-induced p-n junction in single halide perovskite nanowire.

Semiconductor p-n junctions are fundamental building blocks for modern optical and electronic devices. The p- and n-type regions are typically created by chemical doping process. Here we show that in the new class of halide perovskite semiconductors, the p-n junctions can be readily induced through a localized thermal-driven phase transition. We demonstrate this p-n junction formation in a single-crystalline halide perovskite CsSnI3 nanowire (NW). This material undergoes a phase transition from a double-chain yellow (Y) phase to an orthorhombic black (B) phase. The formation energies of the cation and anion vacancies in these two phases are significantly different, which leads to n- and p- type electrical characteristics for Y and B phases, respectively. Interface formation between these two phases and directional interface propagation within a single NW are directly observed under cathodoluminescence (CL) microscopy. Current rectification is demonstrated for the p-n junction formed with this localized thermal-driven phase transition.

Electrical and Optical Tunability in All-Inorganic Halide Perovskite Alloy Nanowires.

Alloying different semiconductors is a powerful approach to tuning the optical and electronic properties of semiconductor materials. In halide perovskites (ABX3), alloys with different anions have been widely studied, and great band gap tunability in the visible range has been achieved. However, perovskite alloys with different cations at the "B" site are less understood due to the synthetic challenges. Herein, we first have developed the synthesis of single-crystalline CsPb xSn1- xI3 nanowires (NWs). The electronic band gaps of CsPb xSn1- xI3 NWs can be tuned from 1.3 to 1.78 eV by varying the Pb/Sn ratio, which leads to the tunable photoluminescence (PL) in the near-infrared range. More importantly, we found that the electrical conductivity increases as more Sn2+ is alloyed with Pb2+, possibly due to the increase of charge carrier concentration when more Sn2+ is introduced. The wide tunability of the optical and electronic properties makes CsPb xSn1- xI3 alloy NWs promising candidates for future optoelectronic device applications.

Ultralow thermal conductivity in all-inorganic halide perovskites.

Controlling the flow of thermal energy is crucial to numerous applications ranging from microelectronic devices to energy storage and energy conversion devices. Here, we report ultralow lattice thermal conductivities of solution-synthesized, single-crystalline all-inorganic halide perovskite nanowires composed of CsPbI3 (0.45 ± 0.05 W·m-1·K-1), CsPbBr3 (0.42 ± 0.04 W·m-1·K-1), and CsSnI3 (0.38 ± 0.04 W·m-1·K-1). We attribute this ultralow thermal conductivity to the cluster rattling mechanism, wherein strong optical-acoustic phonon scatterings are driven by a mixture of 0D/1D/2D collective motions. Remarkably, CsSnI3 possesses a rare combination of ultralow thermal conductivity, high electrical conductivity (282 S·cm-1), and high hole mobility (394 cm2·V-1·s-1). The unique thermal transport properties in all-inorganic halide perovskites hold promise for diverse applications such as phononic and thermoelectric devices. Furthermore, the insights obtained from this work suggest an opportunity to discover low thermal conductivity materials among unexplored inorganic crystals beyond caged and layered structures.

Investigation of phonon coherence and backscattering using silicon nanomeshes.

Phonons can display both wave-like and particle-like behaviour during thermal transport. While thermal transport in silicon nanomeshes has been previously interpreted by phonon wave effects due to interference with periodic structures, as well as phonon particle effects including backscattering, the dominant mechanism responsible for thermal conductivity reductions below classical predictions still remains unclear. Here we isolate the wave-related coherence effects by comparing periodic and aperiodic nanomeshes, and quantify the backscattering effect by comparing variable-pitch nanomeshes. We measure identical (within 6% uncertainty) thermal conductivities for periodic and aperiodic nanomeshes of the same average pitch, and reduced thermal conductivities for nanomeshes with smaller pitches. Ray tracing simulations support the measurement results. We conclude phonon coherence is unimportant for thermal transport in silicon nanomeshes with periodicities of 100 nm and higher and temperatures above 14 K, and phonon backscattering, as manifested in the classical size effect, is responsible for the thermal conductivity reduction.

Thermal Transport in Silicon Nanowires at High Temperature up to 700 K.

Thermal transport in silicon nanowires has captured the attention of scientists for understanding phonon transport at the nanoscale, and the thermoelectric figure-of-merit (ZT) reported in rough nanowires has inspired engineers to develop cost-effective waste heat recovery systems. Thermoelectric generators composed of silicon target high-temperature applications due to improved efficiency beyond 550 K. However, there have been no studies of thermal transport in silicon nanowires beyond room temperature. High-temperature measurements also enable studies of unanswered questions regarding the impact of surface boundaries and varying mode contributions as the highest vibrational modes are activated (Debye temperature of silicon is 645 K). Here, we develop a technique to investigate thermal transport in nanowires up to 700 K. Our thermal conductivity measurements on smooth silicon nanowires show the classical diameter dependence from 40 to 120 nm. In conjunction with Boltzmann transport equation, we also probe an increasing contribution of high-frequency phonons (optical phonons) in smooth silicon nanowires as the diameter decreases and the temperature increases. Thermal conductivity of rough silicon nanowires is significantly reduced throughout the temperature range, demonstrating a potential for efficient thermoelectric generation (e.g., ZT = 1 at 700 K).

Radiative heat transfer in the extreme near field.

Radiative transfer of energy at the nanometre length scale is of great importance to a variety of technologies including heat-assisted magnetic recording, near-field thermophotovoltaics and lithography. Although experimental advances have enabled elucidation of near-field radiative heat transfer in gaps as small as 20-30 nanometres (refs 4-6), quantitative analysis in the extreme near field (less than 10 nanometres) has been greatly limited by experimental challenges. Moreover, the results of pioneering measurements differed from theoretical predictions by orders of magnitude. Here we use custom-fabricated scanning probes with embedded thermocouples, in conjunction with new microdevices capable of periodic temperature modulation, to measure radiative heat transfer down to gaps as small as two nanometres. For our experiments we deposited suitably chosen metal or dielectric layers on the scanning probes and microdevices, enabling direct study of extreme near-field radiation between silica-silica, silicon nitride-silicon nitride and gold-gold surfaces to reveal marked, gap-size-dependent enhancements of radiative heat transfer. Furthermore, our state-of-the-art calculations of radiative heat transfer, performed within the theoretical framework of fluctuational electrodynamics, are in excellent agreement with our experimental results, providing unambiguous evidence that confirms the validity of this theory for modelling radiative heat transfer in gaps as small as a few nanometres. This work lays the foundations required for the rational design of novel technologies that leverage nanoscale radiative heat transfer.

Direct exfoliation of carbon allotropes with structural analogues of self-assembled nanostructures and their photovoltaic applications.

Aromatic amphiphiles were self-assembled into 2-D nanosheets and 1-D nanofibers by systematically varying the volume fraction of the hydrophilic coils, which enabled the direct exfoliation of carbon allotropes with high quality and quantity. A 2-D nanosheet structure was introduced as the hole transporting layer for improving the performance of organic photovoltaic devices.

Electrostatic control of thermoelectricity in molecular junctions.

Molecular junctions hold significant promise for efficient and high-power-output thermoelectric energy conversion. Recent experiments have probed the thermoelectric properties of molecular junctions. However, electrostatic control of thermoelectric properties via a gate electrode has not been possible due to technical challenges in creating temperature differentials in three-terminal devices. Here, we show that extremely large temperature gradients (exceeding 1 × 10(9) K m(-1)) can be established in nanoscale gaps bridged by molecules, while simultaneously controlling their electronic structure via a gate electrode. Using this platform, we study prototypical Au-biphenyl-4,4'-dithiol-Au and Au-fullerene-Au junctions to demonstrate that the Seebeck coefficient and the electrical conductance of molecular junctions can be simultaneously increased by electrostatic control. Moreover, from our studies of fullerene junctions, we show that thermoelectric properties can be significantly enhanced when the dominant transport orbital is located close to the chemical potential (Fermi level) of the electrodes. These results illustrate the intimate relationship between the thermoelectric properties and charge transmission characteristics of molecular junctions and should enable systematic exploration of the recent computational predictions that promise extremely efficient thermoelectric energy conversion in molecular junctions.

Heat dissipation in atomic-scale junctions.

Atomic and single-molecule junctions represent the ultimate limit to the miniaturization of electrical circuits. They are also ideal platforms for testing quantum transport theories that are required to describe charge and energy transfer in novel functional nanometre-scale devices. Recent work has successfully probed electric and thermoelectric phenomena in atomic-scale junctions. However, heat dissipation and transport in atomic-scale devices remain poorly characterized owing to experimental challenges. Here we use custom-fabricated scanning probes with integrated nanoscale thermocouples to investigate heat dissipation in the electrodes of single-molecule ('molecular') junctions. We find that if the junctions have transmission characteristics that are strongly energy dependent, this heat dissipation is asymmetric--that is, unequal between the electrodes--and also dependent on both the bias polarity and the identity of the majority charge carriers (electrons versus holes). In contrast, junctions consisting of only a few gold atoms ('atomic junctions') whose transmission characteristics show weak energy dependence do not exhibit appreciable asymmetry. Our results unambiguously relate the electronic transmission characteristics of atomic-scale junctions to their heat dissipation properties, establishing a framework for understanding heat dissipation in a range of mesoscopic systems where transport is elastic--that is, without exchange of energy in the contact region. We anticipate that the techniques established here will enable the study of Peltier effects at the atomic scale, a field that has been barely explored experimentally despite interesting theoretical predictions. Furthermore, the experimental advances described here are also expected to enable the study of heat transport in atomic and molecular junctions--an important and challenging scientific and technological goal that has remained elusive.

Ultra-high vacuum scanning thermal microscopy for nanometer resolution quantitative thermometry.

Understanding energy dissipation at the nanoscale requires the ability to probe temperature fields with nanometer resolution. Here, we describe an ultra-high vacuum (UHV)-based scanning thermal microscope (SThM) technique that is capable of quantitatively mapping temperature fields with ∼15 mK temperature resolution and ∼10 nm spatial resolution. In this technique, a custom fabricated atomic force microscope (AFM) cantilever, with a nanoscale Au-Cr thermocouple integrated into the tip of the probe, is used to measure temperature fields of surfaces. Operation in an UHV environment eliminates parasitic heat transport between the tip and the sample enabling quantitative measurement of temperature fields on metal and dielectric surfaces with nanoscale resolution. We demonstrate the capabilities of this technique by directly imaging thermal fields in the vicinity of a 200 nm wide, self-heated, Pt line. Our measurements are in excellent agreement with computational results-unambiguously demonstrating the quantitative capabilities of the technique. UHV-SThM techniques will play an important role in the study of energy dissipation in nanometer-sized electronic and photonic devices and the study of phonon and electron transport at the nanoscale.

New organic dye based on a 3,6-disubstituted carbazole donor for efficient dye-sensitized solar cells.

We have synthesized and characterized four organic dyes (H1-H4) based on a 3,6-disubstituted carbazole donor as sensitizers in dye-sensitized solar cells. These dyes have high molar extinction coefficients and energy levels suitable for electron transfer from an electrolyte to nanocrystalline TiO(2) particles. Under standard air mass 1.5 global (AM 1.5 G) solar irradiation, a device using dye H4 exhibits a short-circuit current density (J(sc)) of 13.7 mA cm(-2), an open-circuit voltage (V(oc)) of 0.68 V, a fill factor (FF) of 0.70, and a calculated efficiency of 6.52%. This performance is comparable to that of a reference cell based on N719 (7.30%) under the same conditions. After 1000 hours of visible-light soaking at 60 °C, the overall efficiency remained at 95% of the initial value.

Creation of stable molecular junctions with a custom-designed scanning tunneling microscope.

The scanning tunneling microscope break junction (STMBJ) technique is a powerful approach for creating single-molecule junctions and studying electrical transport in them. However, junctions created using the STMBJ technique are usually mechanically stable for relatively short times (<1 s), impeding detailed studies of their charge transport characteristics. Here, we report a custom-designed scanning tunneling microscope that enables the creation of metal-single molecule-metal junctions that are mechanically stable for more than 1 minute at room temperature. This stability is achieved by a design that minimizes thermal drift as well as the effect of environmental perturbations. The utility of this instrument is demonstrated by performing transition voltage spectroscopy-at the single-molecule level-on Au-hexanedithiol-Au, Au-octanedithiol-Au and Au-decanedithiol-Au junctions.