Controlling the thermoelectric properties of organo-metallic coordination polymers through backbone geometry.

Poly(nickel-benzene-1,2,4,5-tetrakis(thiolate)) (Ni-btt), an organometallic coordination polymer (OMCP) characterized by the coordination between benzene-1,2,4,5-tetrakis(thiolate) (btt) and Ni2+ ions, has been recognized as a promising p-type thermoelectric material. In this study, we employed a constitutional isomer based on benzene-1,2,3,4-tetrakis(thiolate) (ibtt) to generate the corresponding isomeric polymer, poly(nickel-benzene-1,2,3,4-tetrakis(thiolate)) (Ni-ibtt). Comparative analysis of Ni-ibtt and Ni-btt reveals several common infrared (IR) and Raman features attributed to their similar square-planar nickel-sulfur (Ni-S) coordination. Nevertheless, these two polymer isomers exhibit substantially different backbone geometries. Ni-btt possesses a linear backbone, whereas Ni-ibtt exhibits a more undulating, zig-zag-like structure. Consequently, Ni-ibtt demonstrates slightly higher solubility and an increased bandgap in comparison to Ni-btt. The most noteworthy dissimilarity, however, manifests in their thermoelectric properties. While Ni-btt exhibits p-type behavior, Ni-ibtt demonstrates n-type carrier characteristics. This intriguing divergence prompted further investigation into the influence of OMCP backbone geometry on the electronic structure and, particularly, the thermoelectric properties of these materials.

X-Ray-Induced Growth Dynamics of Luminescent Silver Clusters in Zeolites.

Herein, AlKα X-rays are used to drive the growth of luminescent silver clusters in zeolites. The growth of the silver species is tracked using Auger spectroscopy and fluorescence microscopy, by monitoring the evolution from their ions to luminescent clusters and then metallic, dark nanoparticles. It is shown that the growth rate in different zeolites is determined by the mobility of the silver ions in the framework and that the growth dynamics in calcined samples obeys the Hill-Langmuir equation for noncooperative binding. Comparison of the optical properties of X-ray-grown silver clusters with silver clusters formed by standard heat treatment indicates that the latter have a higher specificity toward the formation of luminescent clusters of a specific (small) nuclearity, whereas the former produce a wide distribution of cluster species as well as larger nanoparticles.

Tuning the energetics and tailoring the optical properties of silver clusters confined in zeolites.

The integration of metal atoms and clusters in well-defined dielectric cavities is a powerful strategy to impart new properties to them that depend on the size and geometry of the confined space as well as on metal-host electrostatic interactions. Here, we unravel the dependence of the electronic properties of metal clusters on space confinement by studying the ionization potential of silver clusters embedded in four different zeolite environments over a range of silver concentrations. Extensive characterization reveals a strong influence of silver loading and host environment on the cluster ionization potential, which is also correlated to the cluster's optical and structural properties. Through fine-tuning of the zeolite host environment, we demonstrate photoluminescence quantum yields approaching unity. This work extends our understanding of structure-property relationships of small metal clusters and applies this understanding to develop highly photoluminescent materials with potential applications in optoelectronics and bioimaging.

Luminescent properties of a water-soluble conjugated polymer incorporating graphene-oxide quantum dots.

We report the incorporation of graphene-oxide quantum dots (GOQDs) into films, diluted solutions, and light-emitting diodes (LEDs) as part of a water-soluble derivative of poly(p-phenylene vinylene), or PDV.Li, to investigate their impact on the light-emission properties of this model conjugated polymer. Despite the well-known ability of graphene and graphene oxide to quench the photoluminescence of nearby emitters, we find that the addition of GOQDs to diluted solutions of PDV.Li does not significantly affect the photoluminescence (PL) dynamics of PDV.Li, bringing about only a modest quenching of the PL. However, loading the polymer with GOQDs led to a substantial decrease in the turn-on voltage of LEDs based on GOQD-PDV.Li composites. This effect can be attributed to either the improved morphology of the host polymer, resulting in an increase in the charge mobility, or the enhanced injection through GOQDs near the electrodes.

Bismuth-Based Perovskite Derivates with Thermal Voltage Exceeding 40 mV/K.

Heat is an inexhaustible source of energy, and it can be exploited by thermoelectronics to produce electrical power or electrical responses. The search for a low-cost thermoelectric material that could achieve high efficiencies and can also be straightforwardly scalable has turned significant attention to the halide perovskite family. Here, we report the thermal voltage response of bismuth-based perovskite derivates and suggest a path to increase the electrical conductivity by applying chalcogenide doping. The films were produced by drop-casting or spin coating, and sulfur was introduced in the precursor solution using bismuth triethylxanthate. The physical-chemical analysis confirms the substitution. The sulfur introduction caused resistivity reduction by 2 orders of magnitude, and the thermal voltage exceeded 40 mV K-1 near 300 K in doped and undoped bismuth-based perovskite derivates. X-ray diffraction, Raman spectroscopy, and grazing-incidence wide-angle X-ray scattering were employed to confirm the structure. X-ray photoelectron spectroscopy, elemental analysis, scanning electron microscopy, and energy-dispersive X-ray spectroscopy were employed to study the composition and morphology of the produced thin films. UV-visible absorbance, photoluminescence, inverse photoemission, and ultraviolet photoelectron spectroscopies have been used to investigate the energy band gap.

Polymorphism, fluorescence, and optoelectronic properties of a borazine derivative.

We have prepared a new borazine derivative that bears mesityl substituents at the boron centers and displays exceptional chemical stability. Detailed crystallographic and solid-state fluorescence characterizations revealed the existence of several polymorphs, each of which showed different emission profiles. In particular, a bathochromic shift is observed when going from the lower- to the higher-density crystal. Computational investigations of the conformational dynamics of borazine 1 in both the gas phase and in the solid state using molecular dynamics (MD) simulations showed that the conformation of the peripheral aryl groups significantly varies when going from an isolated molecule (in which the rings are able to flip over the 90° barrier at RT) to the crystals (in which the rotation is locked by packing effects), thus generating specific nonsymmetric intermolecular interactions in the different polymorphs. To investigate the optoelectronic properties of these materials by fabrication and characterization of light-emitting diodes (LEDs) and light-emitting electrochemical cells (LECs), borazine 1 was incorporated as the active material in the emissive layer. The current and radiance versus voltage characteristics, as well as the electroluminescence spectra reported here for the first time are encouraging prospects for the engineering of future borazine-based devices.

Near-infrared polymer light-emitting diodes based on low-energy gap oligomers copolymerized into a high-gap polymer host.

Near-infrared (NIR) polymer light-emitting diodes (PLEDs) based on a fluorene-dioctyloxyphenylene wide-gap host material copolymerized with a low-gap emitter are presented. Various loadings (1, 2.5, 10, 20 mol%) of the low-gap emitter are studied, with higher loadings leading to decreased efficiencies likely due to aggregation effects. While the 10 mol% loading resulted in almost pure NIR emission (>99.6%), the 1 mol% loading yielded optimum device performance, which is among the best reported to date for a unblended single-layer pure polymer emitter, with an external quantum efficiencies of 0.04% emitting at 909 nm. The high spectral purity of the PLEDs combined with their performance support the methodology of copolymerization as an effective strategy for developing NIR PLEDs.

Linear and cyclic porphyrin hexamers as near-infrared emitters in organic light-emitting diodes.

Here we report organic light-emitting diodes incorporating linear and cyclic porphyrin hexamers which have red-shifted emission (λ(PL) = 873 and 920 nm, respectively) compared to single porphyrin rings as a consequence of their extended π-conjugation. We studied the photoluminescence and electroluminescence of blends with poly(9,9'-dioctylfluorene-alt-benzothiadiazole), demonstrating a high photoluminescence quantum efficiency of 7.7% for the linear hexamer when using additives to prevent aggregation and achieving high color purity near-infrared electroluminescence.

High Responsivity Circular Polarized Light Detectors based on Quasi Two-Dimensional Chiral Perovskite Films.

Circularly polarized light (CPL) has considerable technological potential, from quantum computing to bioimaging. To maximize the opportunity, high performance photodetectors that can directly distinguish left-handed and right-handed circularly polarized light are needed. Hybrid organic-inorganic perovskites containing chiral organic ligands are an emerging candidate for the active material in CPL photodetecting devices, but current studies suggest there to be a trade-off between the ability to differentially absorb CPL and photocurrent responsivity in chiral perovskites devices. Here, we report a CPL detector based on quasi two-dimensional (quasi-2D) chiral perovskite films. We find it is possible to generate materials where the circular dichroism (CD) is comparable in both 2D and quasi-2D films, while the responsivity of the photodetector improves for the latter. Given this, we are able to showcase a CPL photodetector that exhibits both a high dissymmetry factor of 0.15 and a high responsivity of 15.7 A W-1. We believe our data further advocates the potential of chiral perovskites in CPL-dependent photonic technologies.

Metal-biomolecule frameworks (BioMOFs): a novel approach for "green" optoelectronic applications.

In this study, a water-stable microcrystalline bioMOF was synthesized, characterized, and loaded with silver ions or highly emissive rare earth (RE) metals such as Eu3+/Tb3+. The obtained materials were used as active layers in a proof-of-concept sustainable light-emitting device, highlighting the potential of bioMOFs in optoelectronic applications.

Local surface potential of π-conjugated nanostructures by Kelvin probe force microscopy: effect of the sampling depth.

Kelvin probe force microscopy (KPFM) is usually applied to map the local surface potential of nanostructured materials at surfaces and interfaces. KPFM is commonly defined as a 'surface technique', even if this assumption is not fully justified. However, a quantification of the surface sensitivity of this technique is crucial to explore electrical properties at the nanoscale. Here a versatile 3D model is presented which provides a quantitative explanation of KPFM results, taking into account the vertical structure of the sample. The model is tested on nanostructured films obtained from two relevant semiconducting systems for field-effect transistor and solar cell applications showing different interfacial properties, i.e., poly(3-hexylthiophene) (P3HT) and perylene-bis-dicarboximide (PDI). These findings are especially important since they enable quantitative determination of the local surface potential of conjugated nanostructures, and thereby pave the way towards optimization of the electronic properties of nanoscale architectures for organic electronic applications.

Dye-catalyst dyads for photoelectrochemical water oxidation based on metal-free sensitizers.

Dye-Sensitized Photoelectrochemical Cells (DS-PECs) have been emerging as promising devices for efficient solar-induced water splitting. In DS-PECs, dyes and catalysts for water oxidation and/or reduction are typically two separate components, thus limiting charge transfer efficiency. A small number of organometallic dyes have been integrated with a catalyst to form an integrated dye-catalyst dyad for photoanodes, but until now no dyads based on metal-free organic dyes have been reported for photoanodes. We herein report the first example of dyad-sensitized photoanodes in DS-PEC water splitting based on metal-free organic dyes and a Ru catalyst. The di-branched donor-π-acceptor dyes carry a donor carbazole moiety which has been functionalized with two different terminal pyridyl ligands in order to coordinate a benchmark Ru complex as a water oxidation catalyst, affording water oxidation dyads. The two dyads have been fully characterized in their optical and electrochemical properties, and XPS has been used to confirm the presence of the catalyst bonded to the dye anchored to the semiconductor anode. The two dyads have been investigated in DS-PEC, showing an excellent faradaic efficiency (88% average across all cells, with a best cell efficiency of 95%), thus triggering new perspectives for the design of efficient molecular dyads based on metal-free dyes for DS-PEC water splitting.

Two-Step Synthesis of Bismuth-Based Hybrid Halide Perovskite Thin-Films.

Lead halide perovskites have been revolutionary in the last decade in many optoelectronic sectors. Their bismuth-based counterparts have been considered a good alternative thanks to their composition of earth-abundant elements, good chemical stability, and low toxicity. Moreover, their electronic structure is in a quasi-zero-dimensional (0D) configuration, and they have recently been explored for use beyond optoelectronics. A significant limitation in applying thin-film technology is represented by the difficulty of synthesizing compact layers with easily scalable methods. Here, the engineering of a two-step synthesis in an air of methylammonium bismuth iodide compact thin films is reported. The critical steps of the process have been highlighted so that the procedure can be adapted to different substrates and application areas.

Self-powered ultrasensitive and highly stretchable temperature-strain sensing composite yarns.

With the emergence of stretchable/wearable devices, functions, such as sensing, energy storage/harvesting, and electrical conduction, should ideally be carried out by a single material, while retaining its ability to withstand large elastic deformations, to create compact, functionally-integrated and autonomous systems. A new class of trimodal, stretchable yarn-based transducer formed by coating commercially available Lycra® yarns with PEDOT:PSS is presented. The material developed can sense strain (first mode), and temperature (second mode) and can power itself thermoelectrically (third mode), eliminating the need for an external power-supply. The yarns were extensively characterized and obtained an ultrahigh (gauge factor ∼3.6 × 105, at 10-20% strain) and tunable (up to about 2 orders of magnitude) strain sensitivity together with a very high strain-at-break point (up to ∼1000%). These PEDOT:PSS-Lycra yarns also exhibited stable thermoelectric behavior (Seebeck coefficient of 15 µV K-1), which was exploited both for temperature sensing and self-powering (∼0.5 µW, for a 10-couple module at ΔT ∼ 95 K). The produced material has potential to be interfaced with microcontroller-based systems to create internet-enabled, internet-of-things type devices in a variety of form factors.

All-Oxide p-n Junction Thermoelectric Generator Based on SnOx and ZnO Thin Films.

Achieving thermoelectric devices with high performance based on low-cost and nontoxic materials is extremely challenging. Moreover, as we move toward an Internet-of-Things society, a miniaturized local power source such as a thermoelectric generator (TEG) is desired to power increasing numbers of wireless sensors. Therefore, in this work, an all-oxide p-n junction TEG composed of low-cost, abundant, and nontoxic materials, such as n-type ZnO and p-type SnOx thin films, deposited on borosilicate glass substrate is proposed. A type II heterojunction between SnOx and ZnO films was predicted by density functional theory (DFT) calculations and confirmed experimentally by X-ray photoelectron spectroscopy (XPS). Moreover, scanning transmission electron microscopy (STEM) combined with energy-dispersive X-ray spectroscopy (EDS) show a sharp interface between the SnOx and ZnO layers, confirming the high quality of the p-n junction even after annealing at 523 K. ZnO and SnOx thin films exhibit Seebeck coefficients (α) of ∼121 and ∼258 µV/K, respectively, at 298 K, resulting in power factors (PF) of 180 µW/m K2 (for ZnO) and 37 µW/m K2 (for SnOx). Moreover, the thermal conductivities of ZnO and SnOx films are 8.7 and 1.24 W/m K, respectively, at 298 K, with no significant changes until 575 K. The four pairs all-oxide TEG generated a maximum power output (Pout) of 1.8 nW (≈126 µW/cm2) at a temperature difference of 160 K. The output voltage (Vout) and output current (Iout) at the maximum power output of the TEG are 124 mV and 0.0146 µA, respectively. This work paves the way for achieving a high-performance TEG device based on oxide thin films.

High charge carrier mobility in solution processed one-dimensional lead halide perovskite single crystals and their application as photodetectors.

Organic inorganic hybrid metal halide perovskites have emerged as promising candidates for photovoltaics and light-emitting diodes. Recently, interest has been growing in the properties of low-dimensional metal halide perovskites, and one-dimensional versions with strong quantum confinement have demonstrated highly efficient broadband luminescence. Nevertheless, the charge transport mechanism in these low dimensional perovskites remains unclear. In this work, we characterised the charge mobility in one-dimensional perovskite single crystals using a space charge limited current method. Temperature dependent charge mobility measurements indicated that localized polarons at high temperature are replaced by delocalized polarons at low temperature with extended states in the polaronic band. A minimum mobility of 4.51 cm2 V-1 s-1 was measured at room temperature. UV photodetectors based on these crystals show an ultrahigh photoresponsivity of 132.3 A W-1. These findings show the promise of high mobility low dimensional perovskite materials for optoelectronic applications.

Full Thermoelectric Characterization of Stoichiometric Electrodeposited Thin Film Tin Selenide (SnSe).

Tin selenide (SnSe) has attracted much attention in the thermoelectric community since the discovery of the record figure of merit (ZT) of 2.6 in single crystal tin selenide in 2014. There have been many reports since of the thermoelectric characterization of SnSe synthesized or manufactured by several methods, but so far none of these have concerned the electrodeposition of SnSe. In this work, stoichiometric SnSe was successfully electrodeposited at -0.50 V vs SCE as shown by EDX, XPS, UPS, and XRD. The full ZT of the electrodeposits were then measured. This was done by both a delamination technique to measure the Seebeck coefficient and electrical conductivity which showed a peak power factor of 4.2 and 5.8 µW m-1 K-2 for the as deposited and heat-treated films, respectively. A novel modified transient 3ω method was used to measure the thermal conductivity of the deposited films on the deposition substrate. This revealed the thermal conductivity to be similar to the ultralow thermal conductivity of single crystal SnSe, with a value of 0.34 W m-1 K-1 being observed at 313 K.

Growth and Characterization of Cu2Zn1-xFexSnS4 Thin Films for Photovoltaic Applications.

Photovoltaics is a promising technology to produce sustainable energy, thanks to the high amount of energy emitted by the sun. One way of having solar cells with low production costs is to apply thin-film technology and with earth-abundant raw materials. A keen interest is arising in kesterite compounds, which are chalcogenides composed of abundant and non-toxic elements. They have already achieved excellent performance at the laboratory level. Here, we report the synthesis and characterization of mixed chalcogenides based on copper, zinc, iron, and tin. Solutions have been studied with different zinc and iron ratios. The distortion of the elementary cell of kesterite increases with the addition of iron until a phase transition to stannite occurs. The process of synthesis and deposition proposed herein is cheap and straightforward, based on the sol-gel technique. These thin films are particularly attractive for use in cheap and easily processable solar cells. The synthesized layers have been characterized by X-ray diffraction, UV-Vis absorption, and Raman, X-ray photoelectron, and energy-dispersive X-ray spectroscopy measurements.

Unusual Thermal Boundary Resistance in Halide Perovskites: A Way To Tune Ultralow Thermal Conductivity for Thermoelectrics.

Halide perovskites have emerged as promising candidates as the active material in photovoltaics and light-emitting diodes. They possess unusual bulk thermal transport properties that have been the focus of a number of studies, but there is much less understanding of thermal transport in thin films where a diverse range of structures and morphologies are accessible. Here, we report on the tuning of in-plane thermal conductivity in methylammonium lead iodide thin films by morphological control. Using 3-ω measurements, we find that the room temperature thermal conductivity of thermally evaporated methylammonium lead iodide perovskite films ranges from 0.31 to 0.59 W/(m K). We measure a discontinuity in thermal conductivity at the orthorhombic-tetragonal phase transition and explore this using density functional theory and attributing it to a collapse in the phonon group velocity along the c-axis of the tetragonal crystal. Moreover, we have quantified the thermal boundary resistance (Kapitza resistance) for thermally evaporated films, allowing us to estimate the Kapitza length, which is 36 ± 2 nm at room temperature and 15 ± 2 nm at 100 K. Curiously, the Kapitza resistance has a strong temperature dependence which we also explore using density functional theory, with these results suggesting an important role of methylammonium rotational modes in scattering phonons at the crystallite boundaries.

Enhanced control of self-doping in halide perovskites for improved thermoelectric performance.

Metal halide perovskites have emerged as promising photovoltaic materials, but, despite ultralow thermal conductivity, progress on developing them for thermoelectrics has been limited. Here, we report the thermoelectric properties of all-inorganic tin based perovskites with enhanced air stability. Fine tuning the thermoelectric properties of the films is achieved by self-doping through the oxidation of tin (ΙΙ) to tin (ΙV) in a thin surface-layer that transfers charge to the bulk. This separates the doping defects from the transport region, enabling enhanced electrical conductivity. We show that this arises due to a chlorine-rich surface layer that acts simultaneously as the source of free charges and a sacrificial layer protecting the bulk from oxidation. Moreover, we achieve a figure-of-merit (ZT) of 0.14 ± 0.01 when chlorine-doping and degree of the oxidation are optimised in tandem.