Search

Hydrogen-bonded (H-bonded) self-assembly is a suitable approach for tailoring the solid-state packing and properties of organic semiconductors. Here we studied the H-bonded self-assembly of an important class of organic semiconductors, diketopyrrolopyrrole (DPP) derivatives, diselenophenylDPP (DSeDPP), dithiazolylDPP (DTzDPP), and dithienothiophenylDPP (DTTDPP), at solid-liquid interfaces using scanning tunneling microscopy (STM) and density functional theory (DFT). At the 1-octanoic acid/highly ordered pyrolytic graphite (HOPG) interface, DSeDPP and DTzDPP either co-assemble with the solvent via H-bonding between lactam and carboxyl groups or form homoassemblies through H-bonding between the lactam groups. However, DTTDPP forms two different homoassemblies involving H-bonding between lactam groups or weak H-bonding between the lactam group and the heteroaromatic ring. Enthalpic factors for the formation of homoassemblies and co-assemblies are investigated by evaluating the inter- and intramolecular interactions in the self-assembled lattices using DFT. A homoassembly with a twisted geometry of molecules with intermolecular π-interactions is only observed for DSeDPP. The absence of homoassembly with the twisted geometry of DTzDPP is attributed to the higher strain energy required to acquire out-of-plane twists in this molecule. Our study shows the profound effects aromatic substituents can impart in the supramolecular assembly of DPP molecules, which influences film morphology and hence its properties ( e.g. charge transport).

Two-dimensional hexagonal boron nitride (2D h-BN) is being extensively studied in optoelectronic devices due to its electronic and photonic properties. However, the controlled optimization of h-BN's insulating properties is necessary to fully explore its potential in energy conversion and storage devices. In this work, we engineered the surface of h-BN nanoflakes via one-step in situ chemical functionalization using a liquid-phase exfoliation approach. The functionalized h-BN (F-h-BN) nanoflakes were subsequently dispersed on the surface of TiO 2 to tune the TiO 2 /QDs interface of the optoelectronic device. The photoelectrochemical (PEC) devices based on TiO 2 /F-h-BN/QDs with optimized addition of carbon nanotubes (CNTs) and scattering layers showed 46% improvement compared to the control device (TiO 2 /QDs). This significant improvement is attributed to the reduced trap/carrier recombination and enhanced carrier injection rate of the TiO 2 -CNTs/F-h-BN/QDs photoanode. Furthermore, by employing an optimized TiO 2 -CNTs/F-h-BN/QDs photoanode, QDs-sensitized solar cells (QDSCs) yield an 18% improvement in photoconversion efficiency. This represents a potential and adaptability of our approach, and pathway to explore surface-engineered 2D materials to optimize the interface of solar energy conversion and other emerging optoelectronic devices.

We report the influence of the partial substitution of Ge with Ti on the properties of NASICON Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) nanofibers prepared by electrospinning. Replacing a small amount of Ge (up to 20%) with Ti is advantageous for enhancing both the purity and morphology of LAGP fibers, as observed by X-ray diffraction, electron microscopy and nuclear magnetic resonance spectroscopy. When Ti-substituted LAGP (LAGTP) fibers are used as filler to develop composite polymer electrolytes, the ionic conductivity at 20 °C improves by a factor of 1.5 compared to the plain polymer electrolyte. Additionally, above 40 °C the LAGTP fiber-based composite electrolytes were more conductive than the equivalent LAGP fiber-based one. We believe that these findings can make a substantial contribution to optimizing current methods and developing novel synthesis approaches for NASICON based electrolytes.

"Giant" core/shell quantum dots (g-QDs) are promising candidates for emerging optoelectronic technologies thanks to their facile structure/composition-tunable optoelectronic properties and outstanding photo-physical/chemical stability. Here, we synthesized a new type of CuInTeSe (CITS)/CdS g-QDs and regulated their optoelectronic properties by controlling the shell thickness. Through increasing the shell thickness, as-prepared g-QDs exhibited tunable red-shifted emission (from 900 to 1200 nm) and prolonged photoluminescence (PL) lifetimes (up to ∼14.0 μs), indicating a formed band structure showing efficient charge separation and transfer, which is further testified by theoretical calculations and ultrafast time-resolved transient absorption (TA) spectroscopy. These CITS/CdS g-QDs with various shell thicknesses can be employed to fabricate photoelectrochemical (PEC) cells, exhibiting improved photoresponse and stability as compared to the bare CITS QD-based devices. The results indicate that the rational design and engineering of g-QDs is very promising for future QD-based optoelectronic technologies.

The formation of ordered molecular structures on surfaces is determined by the balance between molecule-molecule and molecule-substrate interactions. Whether the aggregation process is guided by non-covalent forces or on-surface reactions, a deeper understanding of these interactions is pivotal to formulating a priori predictions of the final structural features and the development of bottom-up fabrication protocols. Theoretical models of molecular systems corroborate the information gathered through experimental observations and help explain the thermodynamic factors that underpin on-surface phase transitions. Here, we report a scanning tunneling microscopy investigation of a tribromo-substituted heterotriangulene on the Au(111) surface, which initially forms an extended close-packed ordered structure stabilized by BrBr halogen bonds when deposited at room temperature. X-ray photoelectron spectroscopy reveals that annealing the self-assembled layer induces a fraction of the molecular precursors to partially dehalogenate that in turn leads to the formation of a less stable BrO non-covalent network which coexists with the short oligomers. Density functional theory (DFT) and Monte Carlo (MC) simulations illustrate how dimer moieties act as defects whose steric hindrance prevents the retention of the more stable configuration. A small number of dimers is sufficient to drive the molecular reorganization into a lower cohesive energy phase. Our study shows the importance of a combined DFT - MC approach to understand the evolution of molecular systems on substrates.

Heterostructured quantum dots (hetero-QDs) have outstanding optical properties and chemical/photostability, which make them promising building blocks for use in various optoelectronic devices. Here, CuInSe x S 2-x /CdSeS/CdS hetero-QDs were synthesized through a facile two-step method. Their particle size, three-dimensional (3D) shapes and the epitaxial relationship between the CuInSe x S 2-x /CdSeS core and CdS shell were investigated by high-resolution transmission electron microscopy (HRTEM). Our investigation proves that the as-synthesized hetero-QDs have a regular tetrahedron 3D shape with four {111} crystal facets. The epitaxial relationship between the CuInSe x S 2-x /CdSeS core and CdS shell is determined to be [110] core //[110] shell , {112} core //{111} shell . In situ HRTEM observations show that the screw dislocation inside the hetero-QDs can be efficiently repaired using e-beam irradiation. These results may help in designing hetero-QDs with high-quality interfaces and identifying the strategies for synthesizing defect-free hetero-QDs.

Ullmann coupling or, more generally, dehalogenative aryl-aryl coupling, is one of the most widely exploited chemical reactions to obtain one- and two-dimensional polymers on metal surfaces. It is generally described as a two-step reaction: (i) dehalogenation, resulting in the formation of a stable intermediate organometallic phase and subsequent (ii) C-C coupling. The topology of the resulting polymer depends on the number and positions of the halogen atoms in the haloaromatic precursor, although its orientation and order are determined by the structure of the intermediate phase. Hitherto, only one intermediate structure, identified as an organometallic (OM) phase, has been reported for such a reaction. Here we demonstrate the formation of two distinct OM phases during the temperature-induced growth of poly(para-phenylene) from 1,4-dibromobenzene precursors on Cu(110). Beyond the already known linear-OM chains, we show that a phase reorganization to a chessboard-like 2D-OM can be activated in a well-defined temperature range. This new intermediate phase, revealed only when the reaction is carried out at low molecular coverages, was characterized by X-ray photoelectron spectroscopy, scanning tunneling microscopy and near-edge X-ray absorption fine structure spectroscopy, and modeled by density functional theory calculations. Our data show that the 2D-OM remains stable after cooling down the sample and is stabilized by four-Cu clusters at each node. The observation of such unexpected intermediate phase shows the complexity of the mechanisms underlying on-surface synthesis and broadens the understanding of Ullmann coupling, which continues to be astonishing despite its extensive use.

Investigating two-dimensional (2D) self-assembled structures of biological monomers governed by intermolecular interactions is a prerequisite to understand the self-assembly of more complex biomolecular systems. 5,6-Dihydroxyindole carboxylic acid (DHICA) is one of the building blocks of eumelanin - an irregular heteropolymer and the most common form of melanin which has potential applications in organic electronics and bioelectronics. By means of scanning tunneling microscopy, density functional theory and Monte Carlo calculations, we investigate DHICA molecular configurations and interactions underlying the multiple 2D patterns formed on Au(111). While DHICA self-assembled molecular networks (SAMNs) are dominated by the hydrogen bonding of carboxylic acid dimers, a variety of 2D architectures are formed due to the multiple weak interactions of the catechol group. The hydroxyl group also allows for redox reactions, caused by oxidation via O2 exposure, resulting in molecular rearrangement. The susceptibility of the molecules to oxidation is affected by their SAMNs architectures, giving insights on the reactivity of indoles as well as highlighting non-covalent assembly as an approach to guide selective oxidation reactions.

Colloidal semiconductor quantum dots (QDs) are promising building blocks for the realization of future optoelectronic technologies, thanks to their size-tunable electronic and optical properties. Among various types of QDs, colloidal "giant" QDs (g-QDs, core/thick-shell) have been widely used in different applications, such as solar cells, light emitting devices, luminescent solar concentrators and photoelectrochemical (PEC) hydrogen production. However, g-QDs have a thick-shell which serves as a physical barrier for electron and hole transfer, leading to a slow charge transfer rate. In this work, we synthesized CdSe/CdSexS1-x/CdS core/shell/shell g-QDs with an intermediate CdSexS1-x alloyed layer. The presence of this interfacial layer largely improves the absorption of CdSe/CdS QDs, particularly in the 300-650 nm range. By engineering the interfacial layer, the holes can leak more into the CdS shell region compared to that of CdSe/CdS QDs. PEC devices based on alloyed g-QDs exhibit a 20% higher saturated photocurrent density (11 ± 0.5 mA cm-2) compared to CdSe/CdS QDs. In addition, after one-hour illumination (100 mW cm-2), the PEC cell based on alloyed g-QDs still exhibits a photocurrent density of 7.5 mA cm-2, maintaining 70% of its initial value. Such alloyed g-QDs are very promising for several emerging optoelectronic applications, where charge separation, transfer and transport play a critical role for the realization of high performance devices.

The ability of catecholamines to undergo oxidative self-polymerization provides an attractive route for preparation of coatings for biotechnology and biomedicine applications. However, efforts toward developing a complete understanding of the mechanism that underpins polymerization have been hindered by the multiple catechol crosslinking reaction pathways that occur during the reaction. Scanning tunneling microscopy allows the investigation of small molecules in a reduced-complexity environment, providing important insight into how the intermolecular forces drive the formation of supramolecular assemblies in a controlled setting. Capitalizing on this approach, we studied the self-assembly of 5,6-dihydroxy-indole (DHI) on Au(111) and Ag(111) to investigate the interactions that affect the two-dimensional growth mechanism and to elucidate the behavior of the catechol group on these two surfaces. X-ray photoelectron spectroscopy, together with density functional theory and Monte Carlo modeling, helps unravel the differences between the two systems. The molecules form large ordered domains, yet with completely different architectures. Our data reveal that some of the DHI molecules deposited on Ag are in a modified redox state, with their catechol group oxidized into quinone. On Ag(111), the molecules are deposited in long-range lamellar patterns stabilized by metal-organic coordination, while covalent dimer pairs are observed on Au(111). We also show that the oxidation susceptibility is affected by the substrate, with the DHI/Au remaining inert even after being exposed to O2 gas.

Photoelectrochemical (PEC) water splitting implementing colloidal quantum dots (QDs) as sensitizers is a promising approach for hydrogen (H2) generation, due to the QD's size-tunable optical properties. However, the challenge of long-term stability of the QDs is still unresolved. Here, we introduce a highly stable QD-based PEC device for H2 generation using a photoanode based on a SnO2-TiO2 heterostructure, sensitized by CdSe/CdS core/thick-shell "giant" QDs. This hybrid photoanode architecture leads to an appreciable saturated photocurrent density of ∼4.7 mA cm-2, retaining an unprecedented ∼96% of its initial current density after two hours, and sustaining ∼93% after five hours of continuous irradiation under an AM 1.5G (100 mW cm-2) simulated solar spectrum. Transient photoluminescence (PL) measurements demonstrate that the heterostructured SnO2-TiO2 photoanode exhibits faster electron transfer compared with the bare TiO2 photoanode. The lower electron transfer rate in the TiO2 photoanode can be attributed to slow electron kinetics in the ultraviolet regime, revealed by ultrafast transient absorption spectroscopy. Graphene microplatelets were further introduced into the heterostructured photoanode, which boosted the photocurrent density to ∼5.6 mA cm-2. Our results demonstrate that the SnO2-TiO2 heterostructured photoanode holds significant potential for developing highly stable PEC cells.

Lanthanide-doped upconverting nanoparticles (UCNPs) have been studied for diverse biomedical applications due to their inherent ability to convert near-infrared (NIR) excitation light to higher energies (spanning the ultraviolet, visible, and NIR regions). To explore additional functionalities, rational combination with other optically active nanostructures may lead to the development of new multimodal nanoplatforms with theranostic (therapy and diagnostic) capabilities. Here, we develop a nanocomposite consisting of NaGdF 4 :Er 3+ , Yb 3+ UCNPs, mesoporous silica (SiO 2 ), gold nanorods (GNRs) and a photosensitizer, with integrated functionalities including luminescence imaging, photothermal generation, nanothermometry and photodynamic effects. Under 980 nm irradiation, GNRs and UCNPs are simultaneously excited due to the overlap between the surface plasmon resonance of the GNRs and the absorption of the UCNPs leading to plasmonic enhancement of the upconverted luminescence, while concomitantly creating a temperature gradient. The temperature increase can be determined from the intensity ratio of the upconverted green emission of the UCNPs. Finally, a photosensitizer, zinc phthalocyanine, was loaded into the mesoporous SiO 2 . Upon laser irradiation, the upconverted visible light subsequently activates the photosensitizer to release reactive oxygen species. The multifunctional GNR@SiO 2 @UCNPs nanocomposites showed strong luminescence signal when incubated in HeLa cervical cancer cells, making them ideal bioprobes for future theranostic applications.

We designed a facile approach for the synthesis of PbS quantum dots (QDs) using thiourea and lead acetate as sources of sulfur and lead, respectively. The sizes of the PbS QDs could be systematically controlled by simply adjusting the reaction parameters. Cd post-treatment via a cation exchange method was performed to increase the stability of QDs. As a proof of concept, colloidal PbS QDs synthesized by using air-stable thiourea were employed as light harvesters for both (i) solar driven photoelectrochemical (PEC) hydrogen generation and (ii) QDs sensitized solar cells (QDSSCs). For PEC hydrogen generation, similar saturated photocurrent densities are observed by using thiourea compared to bis(trimethylsilyl) sulfide, which is air-sensitive and unstable. For QDSSCs, the devices fabricated with QDs synthesized from thiourea reveal a better performance compared to devices fabricated with QDs synthesized from traditional bis(trimethylsilyl) sulfide. Our work demonstrates that this synthetic method is a promising alternative to the existing methodologies of PbS QDs and holds great potential for future solar technologies.

Materials offering excellent mechanical flexibility, high electrical conductivity and electromagnetic interference (EMI) attenuation with minimal thickness are in high demand, particularly if they can be easily processed into films. Carbon nanotube films deposited on a PDMS substrate combine these requirements. In this work, the potential of single wall carbon nanotubes (SWCNT) deposited on flexible polydimethylsiloxane (PDMS) polymer substrates for EMI attenuation is demonstrated. A 6-micrometer-thick SWCNT film exhibits EMI shielding effectiveness of 24.5 decibels in the extreme high frequency band (EHF), reaching 40 decibels when the SWCNTs are N-doped, which is one of the highest specific EMI attenuation performances optimized with film thickness realized to date. This performance stems from the good electrical conductivity of N-SWCNT films (150 Siemens per centimeter) and possible internal multireflections within the SWCNTs network. The excellent mechanical flexibility and easy coating processing enable them to sheathe complex shaped surfaces while providing high electromagnetic interference attenuation efficiency.

Nanostructured magnetic materials with well-defined magnetic anisotropy are very promising as building blocks in spintronic devices that operate at room temperature. Here we demonstrate the epitaxial growth of highly oriented Fe 3 O 4 nanorods on a SrTiO 3 substrate by hydrothermal synthesis without the use of a seed layer. The epitaxial nanorods showed biaxial magnetic anisotropy with an order of magnitude difference between the anisotropy field values of the easy and hard axes. Using a combination of conventional magnetometry, transverse susceptibility, magnetic force microscopy (MFM) and magneto-optic Kerr effect (MOKE) measurements, we investigate magnetic behavior such as temperature dependent magnetization and anisotropy, along with room temperature magnetic domain formation and its switching. The interplay of epitaxy and enhanced magnetic anisotropy at room temperature, with respect to randomly oriented powder Fe 3 O 4 nanorods, is discussed. The results obtained identify epitaxial nanorods as useful materials for magnetic data storage and spintronic devices that necessitate tunable anisotropic properties with sharp magnetic switching phenomena.

Semiconducting nanocrystals optically active in the infrared region of the electromagnetic spectrum enable exciting avenues in fundamental research and novel applications compatible with the infrared transparency windows of biosystems such as chemical and biological optical sensing, including nanoscale thermometry. In this context, quantum dots (QDs) with double color emission may represent ultra-accurate and self-calibrating nanosystems. We present the synthesis of giant core/shell/shell asymmetric QDs having a PbS/CdS zinc blende (Zb)/CdS wurtzite (Wz) structure with double color emission close to the near-infrared (NIR) region. We show that the double emission depends on the excitation condition and analyze the electron-hole distribution responsible for the independent and simultaneous radiative exciton recombination in the PbS core and in the CdS Wz shell, respectively. These results highlight the importance of the driving force leading to preferential crystal growth in asymmetric QDs, and provide a pathway for the rational control of the synthesis of double color emitting giant QDs, leading to the effective exploitation of visible/NIR transparency windows.

We demonstrate the promising potential of using perovskite Bi2FeCrO6 (BFCO) for niche applications in photovoltaics (PV) (e.g. self-powered sensors that simultaneously exploit PV conversion and multiferroic properties) or as a complement to mature PV technologies like silicon. BFCO thin films were epitaxially grown on silicon substrates using an MgO buffer layer. Piezoresponse force microscopy measurements revealed that the tensile strained BFCO phase exhibits a polarization predominantly oriented through the in-plane direction. The semiconducting bandgap of the ordered BFCO phase combined with ferroelectric properties, opens the possibility of a ferroelectric PV efficiency above 2% in a thin film device and the use of ferroelectric materials simultaneously as solar absorber layers and carrier separators in PV devices. A large short circuit photocurrent density of 13.8 mA cm(-2) and a photovoltage output of 0.5 V are typically obtained at FF of 38% for BFCO devices fabricated on silicon. We believe that the reduced photovoltage is due to the low diffusion length of photogenerated charge carriers in the BFCO material where the ferroelectric domains are predominately oriented in-plane and thus do not contribute efficiently to the photocharge separation process.

Hollow ceria-based composites, which consist of noble metal nanoparticles or metal oxides as a secondary component, are being studied extensively for potential applications in heterogeneous catalysis. This is due to their unique features, which exhibit the advantages of a hollow structure (e.g. high surface area and low weight), and also integrate the properties of ceria and noble metals/metal oxides. More importantly, the synergistic effect between constituents in hollow ceria-based composites has been demonstrated in various catalytic reactions. In this feature article, we summarize the state-of-the-art in the synthesis of hollow ceria-based composites, including traditional hard-templates and more recently, sacrificial-template engaged strategies, highlighting the key role of selected templates in the formation of hollow composites. In addition, the catalytic applications of hollow ceria-based composites are briefly surveyed. Finally, challenges and perspectives on future advances of hollow ceria-based composites are outlined.

Lanthanide-doped upconverting nanoparticles (UCNPs), which convert near-infrared (NIR) light to higher energy light have been intensively studied for theranostic applications. Here, we developed a hybrid core/shell nanocomposite with multifunctional properties using a multistep strategy consisting of a gold nanorod (GNR) core with an upconverting NaYF4:Er3+, Yb3+ shell (GNR@NaYF4:Er3+, Yb3+). To use a single excitation beam, the GNR plasmon was tuned to ∼650 nm, which is resonant with the upconverted red Er3+ emission emanating from the 4F9/2 excited state. Thus, under laser irradiation at 980 nm, the intensity ratio of the upconverted green emission (arising from the 2H11/2 and 4S3/2 excited states of Er3+) showed a remarkable thermal sensitivity, which was used to calculate the temperature change due to rapid heat conversion from the GNR core. The red upconversion emission of the GNR@NaYF4:Er3+, Yb3+ core/shell nanocomposite decreased compared with the NaYF4:Er3+, Yb3+ nanoshell structure (without a GNR core), which indicates that energy transfer from NaYF4:Er3+, Yb3+ to the GNR takes place, subsequently causing a photothermal effect. The anticancer drug, doxorubicin, was loaded into the GNR@NaYF4:Er3+, Yb3+ nanocomposites and the drug release profile was evaluated. In particular, the release of doxorubicin was significantly enhanced at lower pH and higher temperature caused by the photothermal effect. This multifunctional nanocomposite, which is suitable for local heating and controlled drug release, shows strong potential for use in cancer therapy.

We investigate, using scanning tunnelling microscopy, the adsorption of pentacene on Ni(111) at room temperature and the behaviour of these monolayer films with annealing up to 700 °C. We observe the conversion of pentacene into graphene, which begins from as low as 220 °C with the coalescence of pentacene molecules into large planar aggregates. Then, by annealing at 350 °C for 20 minutes, these aggregates expand into irregular domains of graphene tens of nanometers in size. On surfaces where graphene and nickel carbide coexist, pentacene shows preferential adsorption on the nickel carbide phase. The same pentacene to graphene transformation was also achieved on Cu(111), but at a higher activation temperature, producing large graphene domains that exhibit a range of moiré superlattice periodicities.

We report a new method for the growth of reduced graphene oxide (rGO) on the 316L alloy of stainless steel (SS) and its relevance for biomedical applications. We demonstrate that electrochemical etching increases the concentration of metallic species on the surface and enables the growth of rGO. This result is supported through a combination of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM), density functional theory (DFT) calculations and static water contact angle measurements. Raman spectroscopy identifies the G and D bands for oxidized species of graphene at 1595 cm(-1) and 1350 cm(-1), respectively, and gives an ID/IG ratio of 1.2, indicating a moderate degree of oxidation. XPS shows -OH and -COOH groups in the rGO stoichiometry and static contact angle measurements confirm the wettability of rGO. SEM and AFM measurements were performed on different substrates before and after coronene treatment to confirm rGO growth. Cell viability studies reveal that these rGO coatings do not have toxic effects on mammalian cells, making this material suitable for biomedical and biotechnological applications.

N-type metal oxide solar cells sensitized by infrared absorbing PbS quantum dots (QDs) represent a promising alternative to traditional photovoltaic devices. However, colloidal PbS QDs capped with pure organic ligand shells suffer from surface oxidation that affects the long term stability of the cells. Application of a passivating CdS shell guarantees the increased long term stability of PbS QDs, but can negatively affect photoinduced charge transfer from the QD to the oxide and the resulting photoconversion efficiency (PCE). For this reason, the characterization of electron injection rates in these systems is very important, yet has never been reported. Here we investigate the photoelectron transfer rate from PbS@CdS core@shell QDs to wide bandgap semiconducting mesoporous films using photoluminescence (PL) lifetime spectroscopy. The different electron affinity of the oxides (SiO2, TiO2 and SnO2), the core size and the shell thickness allow us to fine tune the electron injection rate by determining the width and height of the energy barrier for tunneling from the core to the oxide. Theoretical modeling using the semi-classical approximation provides an estimate for the escape time of an electron from the QD 1S state, in good agreement with experiments. The results demonstrate the possibility of obtaining fast charge injection in near infrared (NIR) QDs stabilized by an external shell (injection rates in the range of 110-250 ns for TiO2 films and in the range of 100-170 ns for SnO2 films for PbS cores with diameters in the 3-4.2 nm range and shell thickness around 0.3 nm), with the aim of providing viable solutions to the stability issues typical of NIR QDs capped with pure organic ligand shells.

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.

Diatoms are one of the most successful photosynthetic organisms and given the important role that their shells (frustules) play in light trapping we explored their use in multilayered materials for application as photoanodes in dye sensitised solar cells (DSSCs). We find a substantial improvement in energy conversion efficiency of 30%, increasing from 3.5% to 4.6% with diatom incorporation.

Weak interactions between bromine, sulphur, and hydrogen are shown to stabilize 2D supramolecular monolayers at the liquid-solid interface. Three different thiophene-based semiconducting organic molecules assemble into close-packed ultrathin ordered layers. A combination of scanning tunneling microscopy (STM) and density functional theory (DFT) elucidates the interactions within the monolayer. Electrostatic interactions are identified as the driving force for intermolecular Br···Br and Br···H bonding. We find that the SS interactions of the 2D supramolecular layers correlate with the hole mobilities of thin film transistors of the same materials.

We report the control of the growth mode of Bi(2)FeCrO(6) thin and ultrathin films by either tuning the pulsed laser deposition parameters or by using a buffer layer. The films are epitaxial and the heterostructures exhibit very smooth interfaces, thus eliminating the main obstacle in the realization of tunnel junctions. By characterizing the functional properties of thin films we find that Bi(2)FeCrO(6) retains its room temperature multiferroic character even at the nanoscale. The coexistence of these properties in ultra-thin Bi(2)FeCrO(6) films will pave the way to design multifunctional devices for applications in spintronics and electronics, such as ferroelectric tunnel junctions or magnetic tunnel junctions with ferroelectric barriers.

Due to its remarkable mechanical and biological properties, there is considerable interest in understanding, and replicating, spider silk's stress-processing mechanisms and structure-function relationships. Here, we investigate the role of water in the nanoscale mechanics of the different regions in the spider silk fibre, and their relative contributions to stress processing. We propose that the inner core region, rich in spidroin II, retains water due to its inherent disorder, thereby providing a mechanism to dissipate energy as it breaks a sacrificial amide-water bond and gains order under strain, forming a stronger amide-amide bond. The spidroin I-rich outer core is more ordered under ambient conditions and is inherently stiffer and stronger, yet does not on its own provide high toughness. The markedly different interactions of the two proteins with water, and their distribution across the fibre, produce a stiffness differential and provide a balance between stiffness, strength and toughness under ambient conditions. Under wet conditions, this balance is destroyed as the stiff outer core material reverts to the behaviour of the inner core.

Spider silk shows great potential as a biomaterial: in addition to biocompatibility and biodegradability, its strength and toughness are greater than native biological fibres (e.g. collagen), with toughness exceeding that of synthetic fibres (e.g. nylon). Although the ultimate tensile strength and toughness at failure are unlikely to be limiting factors, its yield strain of 2% is insufficient, particularly for biomedical application because of the inability to mimic the complex ultrastructure of natural tissues with current tissue engineering approaches. To harness the full potential of spider silk as a biomaterial, it is therefore necessary to increase its yield strain. In this paper, we discuss the means by which the mechanical properties of spider silk, particularly the yield strain, can be optimized through structural modifications.

Among the carbon allotropes newly discovered during the last few decades, carbon nanotubes (CNTs) have attracted enormous attention due to their structural and electronic properties with strong one dimensional character. The physical and chemical features of such systems are intrinsically rich and complex, and can only be probed by using multiple experimental and theoretical techniques. In this feature, we focus on the structural and electronic properties of CNTs that can be accessed by using transmission electron energy loss spectroscopies. The latter are complementary to optical and X-ray absorption techniques, yet allow to obtain the electronic structure with nanoscale spatial resolution. An improved understanding of the structure-electronic properties relationship of these unique 1D systems would represent a fundamental advance, and holds the promise of using CNTs in future applications.