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Ion scattering spectroscopy (ISS) is an analytical tool that provides direct structural, topographical, and atomic compositional information at interfaces when ions are used as projectiles. Since its development in 1967, ISS is commonly used to obtain quantitative information about solid interfaces. Over the last couple of decades, ISS has emerged as an important technique to probe liquid interfaces and their studies employing ISS has become not uncommon, more so with Neutral impact collision ion scattering spectroscopy (NICISS). Therefore, here the principle of ISS with a particular focus on NICISS and its data evaluation are summarised while reviewing some important studies at vapor-liquid interfaces that provide direct information for molecular orientation of liquids (including ionic liquids), composition and distribution of atoms (or solutes) and charges as a function of depth to gain vast variety of thermodynamical information. Employing ISS such information can be achieved with high depth resolution of ∼1-2 Å (depending on the nature of the experiment). These examples highlight the significance of ISS and show potential for its application for studies related to specific ion effects, atmospheric reaction in aerosol and sea water droplets, and even determining the fate of environmental pollutants like heavy metal ions and per-fluoroalkyl substances (PFAS). Furthermore, some limitations of ISS are also discussed relating to investigation of high-vapor pressure liquids and probing buried interfaces like liquid-liquid interfaces while presenting progresses made in probing solid-liquid interfaces., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Self-assembled monolayers (SAMs), such as alkanethiols (AT), are widely used as functional coatings or interfaces between different materials. There is an assumption that the arrangement and alignment of the hydrocarbon chains in films made from carboxyl-terminated alkanethiols are similar to those made from alkanethiols. Here, the structure of the outermost layer and near-surface region of SAMs formed from carboxyl-terminated alkanethiols of various lengths has been analyzed. The chemical composition of the samples was measured using X-ray photoelectron spectroscopy (XPS) and angle-resolved XPS (AR-XPS), allowing the film thickness. Metastable induced photoelectron spectroscopy (MIES) as a surface analytical tool sensitive only for the outermost layer in conjunction with density functional theory (DFT) calculations provided insights into the composition of the topmost layer, showing that it consists mainly of the backbone of the SAM-forming molecules. Through combining AR-XPS concentration depth profiles and the measurement of the composition of the outermost layer, it can be shown that SAMs tend to favor a gauche orientation, enabling interactions between the functional groups.

Electrolytes are central to many technological applications, as well as life itself. The behavior and properties of electrolytes are often described in terms of ion pairs, whereby ions associate as either contact ion pairs (in which ions are "touching") solvent-separated ion pairs (in which ions' solvent shells overlap) or solvent-solvent-separated ion pairs (in which ions' solvent shells are distinct). However, this paradigm is generally restricted to statistically averaged descriptions of solution structure and ignores temporal behavior. Here we elucidate the time-resolved dynamics of these ion-ion interactions in aqueous metal chloride electrolytes using the partial van Hove correlation function, based on polarizable molecular dynamics simulations. Our results show that the existence and persistence of ion pairs in aqueous metal chloride electrolytes should not be assumed a priori, but in fact are ion specific features of the solution with lifetimes on subpicosecond time scales.

Ru is a metal of interest in catalysis. Monodisperse Ru 3 clusters as catalytic sites are relevant for the development of catalysts because clusters use significantly lower amounts of precious materials for forming active sites due to the small size of the cluster. However, retaining the mono-dispersity of the cluster size after deposition is a challenge because surface energy could drive both agglomeration and encapsulation of the clusters. In the present work Ru 3 clusters are deposited by chemical vapor deposition (CVD) of Ru 3 (CO) 12 and cluster source depositions of bare Ru 3 onto radio frequency sputter-deposited TiO 2 (RF-TiO 2 ) substrates, TiO 2 (100), and SiO 2 . When supported on RF-TiO 2 , bare Ru 3 is encapsulated by a layer of titania substrate material during deposition with a cluster source. Ligated Ru 3 (CO) 12 is also encapsulated by a layer of titania when deposited onto sputter-treated RF-TiO 2 , but only through heat treatment which is required to remove most of the ligands. The titania overlayer thickness was determined to be 1-2 monolayers for Ru 3 (CO) 12 clusters on RF-TiO 2 , which is thin enough for catalytic or photocatalytic reactions to potentially occur even without clusters being part of the very outermost layer. The implication for catalysis of the encapsulation of Ru 3 into the RF-TiO 2 is discussed. Temperature-dependent X-ray photoelectron spectroscopy (XPS), angle-resolved XPS, and temperature-dependent low energy ion scattering (TD-LEIS) are used to probe how the cluster-surface interaction changes due to heat treatment and scanning transmission electron microscopy (STEM) was used to image the depth of the surface from side-on.

Within recent years, there has been an increased interest towards organic photovoltaics (OPVs), especially with their significant device performance reaching beyond 19% since 2022. With these advances in the device performance of laboratory-scaled OPVs, there has also been more attention directed towards using printing and coating methods that are compatible with large-scale fabrication. Though large-area (>100 cm 2 ) OPVs have reached an efficiency of 15%, this is still behind that of laboratory-scale OPVs. There also needs to be more focus on determining strategies for improving the lifetime of OPVs that are suitable for scalable manufacturing, as well as methods for reducing material and manufacturing costs. In this paper, we compare several printing and coating methods that are employed to fabricate OPVs, with the main focus towards the deposition of the active layer. This includes a comparison of performances at laboratory (<1 cm 2 ), small (1-10 cm 2 ), medium (10-100 cm 2 ), and large (>100 cm 2 ) active area fabrications, encompassing devices that use scalable printing and coating methods for only the active layer, as well as "fully printed/coated" devices. The article also compares the research focus of each of the printing and coating techniques and predicts the general direction that scalable and large-scale OPVs will head towards.

Metallic lithium (Li) is the most attractive anode for Li batteries because it holds the highest theoretical specific capacity (3860 mA h g -1 ) and the lowest redox potential (-3.040 V vs SHE). However, the poor interface stability of the Li anode, which is caused by the high reactivity and dendrite formation of metallic Li upon cycling, leads to undesired electrochemical performance and safety issues. While two-dimensional boron nitride (BN) nanosheets have been utilized as an interfacial layer, the mechanism on how they stabilize the Li-electrolyte interface remains elusive. Here, we show how BN nanosheet interlayers suppress Li dendrite formation, enhance Li ion transport kinetics, facilitate Li deposition, and reduce electrolyte decomposition. We show through both simulation and experimental data that the desolvation process of a solvated Li ion within the interlayer nanochannels kinetically favors Li deposition. This process enables long cycling stability, reduced voltage polarization, improved interface stability, and negligible volume expansion. Their application as an interfacial layer in symmetric cells and full cells that display significantly improved electrochemical properties is also demonstrated. The knowledge gained in this study provides both critical insights and practical guidelines for designing a Li metal anode with significantly improved performance.

Employing neutral impact collision ion scattering spectroscopy (NICISS), we have directly measured the concentration depth profiles (CDPs) of various monovalent ions at the vapor-formamide interface. NICISS provides CDPs of individual ions by measuring the energy loss of neutral helium atoms backscattered from the solution interface. CDPs at the vapor-formamide interface of Cl - , Br - , I - , Na + , K + , and Cs + are measured and compared to elucidate the interfacial specific ion trends. We report a reverse Hofmeister series in the presence of inorganic ions (anion and cation) at the vapor-formamide interface relative to the water-vapor interface, and the CDPs are found to be independent of the counterion for most ions studied. Thus, ions at the surface of formamide follow a "Hofmeister paradigm" where the counterion does not impact the ion series. These specific ion trends are complemented with surface tension and X-ray absorption near-edge structure (XANES) measurements on formamide electrolyte solutions.

Chromium oxide (Cr 2 O 3 ) is a beneficial metal oxide used to prevent the backward reaction in photocatalytic water splitting. The present work investigates the stability, oxidation state, and the bulk and surface electronic structure of Cr-oxide photodeposited onto P25, BaLa 4 Ti 4 O 15 , and Al:SrTiO 3 particles as a function of the annealing process. The oxidation state of the Cr-oxide layer as deposited is found to be Cr 2 O 3 on the surface of P25 and Al:SrTiO 3 particles and Cr(OH) 3 on BaLa 4 Ti 4 O 15 . After annealing at 600 °C, for P25 (a mixture of rutile and anatase TiO 2 ), the Cr 2 O 3 layer diffuses into the anatase phase but remains at the surface of the rutile phase. For BaLa 4 Ti 4 O 15 , Cr(OH) 3 converts to Cr 2 O 3 upon annealing and diffuses slightly into the particles. However, for Al:SrTiO 3 , the Cr 2 O 3 remains stable at the surface of the particles. The diffusion here is due to the strong metal-support interaction effect. In addition, some of the Cr 2 O 3 on the P25, BaLa 4 Ti 4 O 15 , and Al:SrTiO 3 particles is reduced to metallic Cr after annealing. The effect of Cr 2 O 3 formation and diffusion into the bulk on the surface and bulk band gaps is investigated with electronic spectroscopy, electron diffraction, DRS, and high-resolution imaging. The implications of the stability and diffusion of Cr 2 O 3 for photocatalytic water splitting are discussed.

We investigated the effect of adding p -anisaldehyde (AA) solvent to the ink containing poly[[2,60-4,8-di(5-ethylhexylthienyl)benzo[1,2-b:3,3-b]dithiophene][3-fluoro-2[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]](PTB7-Th) and 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:20,30-d0]-s-indaceno[1,2-b:5,6-b0]-dithiophene(ITIC) on the morphology of the active layer. The present study focuses on determining the effect of the additive on the compositions at the surface of the PTB7-Th: ITIC composite and its morphology, forming one side of the interface of the blend with the MoO X electrode, and the influence of the structural change on the performance of devices. Studies of device performance show that the addition of the additive AA leads to an improvement in device performance. Upon the addition of AA, the concentration of PTB7-Th at the surface of the bulk heterojunction (BHJ) increases, causing an increase in surface roughness of the surface of the BHJ. This finding contributes to an understanding of the interaction between the donor material and high work function electrode/interface material. The implications for the interface are discussed.

Radio frequency (RF) magnetron sputtering allows the fabrication of TiO 2 films with high purity, reliable control of film thickness, and uniform morphology. In the present study, the change in surface roughness upon heating two different thicknesses of RF sputter-deposited TiO 2 films was investigated. As a measure of the process of the change in surface morphology, chemically -synthesised phosphine-protected Au 9 clusters covered by a photodeposited CrO x layer were used as a probe. Subsequent to the deposition of the Au 9 clusters and the CrO x layer, samples were heated to 200 ℃ to remove the triphenylphosphine ligands from the Au 9 cluster. After heating, the thick TiO 2 film was found to be mobile, in contrast to the thin TiO 2 film. The influence of the mobility of the TiO 2 films on the Au 9 clusters was investigated with X-ray photoelectron spectroscopy. It was found that the high mobility of the thick TiO 2 film after heating leads to a significant agglomeration of the Au 9 clusters, even when protected by the CrO x layer. The thin TiO 2 film has a much lower mobility when being heated, resulting in only minor agglomeration of the Au 9 clusters covered with the CrO x layer.

Specific ion effects (SIE), encompassing the Hofmeister Series, have been known for more than 130 years since Hofmeister and Lewith's foundational work. SIEs are ubiquitous and are observed across the medical, biological, chemical and industrial sciences. Nevertheless, no general predictive theory has yet been able to explain ion specificity across these fields; it remains impossible to predict when, how, and to what magnitude, a SIE will be observed. In part, this is due to the complexity of real systems in which ions, counterions, solvents and cosolutes all play varying roles, which give rise to anomalies and reversals in anticipated SIEs. Herein we review the historical explanations for SIE in water and the key ion properties that have been attributed to them. Systems where the Hofmeister series is perturbed or reversed are explored, as is the behaviour of ions at the liquid-vapour interface. We discuss SIEs in mixed electrolytes, nonaqueous solvents, and in highly concentrated electrolyte solutions - exciting frontiers in this field with particular relevance to biological and electrochemical applications. We conclude the perspective by summarising the challenges and opportunities facing this SIE research that highlight potential pathways towards a general predictive theory of SIE.

Atomically precise gold clusters are highly desirable due to their well-defined structure which allows the study of structure-property relationships. In addition, they have potential in technological applications such as nanoscale catalysis. The structural, chemical, electronic, and optical properties of ligated gold clusters are strongly defined by the metal-ligand interaction and type of ligands. This critical feature renders gold-phosphine clusters unique and distinct from other ligand-protected gold clusters. The use of multidentate phosphines enables preparation of varying core sizes and exotic structures beyond regular polyhedrons. Weak gold-phosphorous (Au-P) bonding is advantageous for ligand exchange and removal for specific applications, such as catalysis, without agglomeration. The aim of this review is to provide a unified view of gold-phosphine clusters and to present an in-depth discussion on recent advances and key developments for these clusters. This review features the unique chemistry, structural, electronic, and optical properties of gold-phosphine clusters. Advanced characterization techniques, including synchrotron-based spectroscopy, have unraveled substantial effects of Au-P interaction on the composition-, structure-, and size-dependent properties. State-of-the-art theoretical calculations that reveal insights into experimental findings are also discussed. Finally, a discussion of the application of gold-phosphine clusters in catalysis is presented., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Sputtered NiO x (sp-NiO x ) is a preferred hole transporting material for perovskite solar cells because of its hole mobility, ease of manufacturability, good stability, and suitable Fermi level for hole extraction. However, uncontrolled defects in sp-NiO x can limit the efficiency of solar cells fabricated with this hole transporting layer. An interfacial layer has been proposed to modify the sp-NiO x /perovskite interface, which can contribute to improving the crystallinity of the perovskite film. Herein, a 2-(3,6-dimethoxy-9 H -carbazol-9-yl)ethyl]phosphonic acid (MeO-2PACz) self-assembled monolayer was used to modify an sp-NiO x surface. We found that the MeO-2PACz interlayer improves the quality of the perovskite film due to an enlarged domain size, reduced charge recombination at the sp-NiO x /perovskite interface, and passivation of the defects in sp-NiO x surfaces. In addition, the band tail states are also reduced, as indicated by photothermal deflection spectroscopy, which thus indicates a reduction in defect levels. The overall outcome is an improvement in the device efficiency from 11.9% to 17.2% due to the modified sp-NiO x /perovskite interface, with an active area of 1 cm 2 (certified efficiency of 16.25%). On the basis of these results, the interfacial engineering of the electronic properties of sp-NiO x /MeO-2PACz/perovskite is discussed in relation to the improved device performance., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The properties of semiconductor surfaces can be modified by the deposition of metal clusters consisting of a few atoms. The properties of metal clusters and of cluster-modified surfaces depend on the number of atoms forming the clusters. Deposition of clusters with a monodisperse size distribution thus allows tailoring of the surface properties for technical applications. However, it is a challenge to retain the size of the clusters after their deposition due to the tendency of the clusters to agglomerate. The agglomeration can be inhibited by covering the metal cluster modified surface with a thin metal oxide overlayer. In the present work, phosphine-protected Au clusters, Au 9 (PPh 3 ) 8 (NO 3 ) 3 , were deposited onto RF-sputter deposited TiO 2 films and subsequently covered with a Cr 2 O 3 film only a few monolayers thick. The samples were then heated to 200 °C to remove the phosphine ligands, which is a lower temperature than that required to remove thiolate ligands from Au clusters. It was found that the Cr 2 O 3 covering layer inhibited cluster agglomeration at an Au cluster coverage of 0.6% of a monolayer. When no protecting Cr 2 O 3 layer was present, the clusters were found to agglomerate to a large degree on the TiO 2 surface.

Surface defects influence the dye adsorption on TiO 2 used as a substrate in dye-sensitized solar cells (DSSCs). In this study, we have used different Ar + sputtering doses to create a controlled density of defects on a TiO 2 surface exposed to different pre-heating temperatures in order to analyse the influence of defects on the N719 dye adsorption. TiO 2 was pre-treated using two different treatments. The first treatment involved heating to 200 °C with subsequent sputtering at different doses. The second treatment included heating only, but at four different temperatures starting at 200 °C. After the pre-treatments, the TiO 2 samples were immersed into an N719 dye solution for 24 hours at room temperature to dye the TiO 2 substrates. The amount of Ti 3+ surface defects introduced by the different pre-treatments and their influence on dye adsorption onto the TiO 2 surface were examined by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES). Neutral impact collision ion scattering spectroscopy (NICISS) was used to determine the coverage of the TiO 2 surface by adsorbed dye molecules. It was found that Ti 3+ surface defects were formed by Ar + sputtering but not by pre-treatment through heating alone. MIES analysis of the outer-most layer and density of states calculations show that the thiocyanate ligand of the N719 dye becomes directed away from the TiO 2 surface. Both XPS and NICISS results indicate that the amount of adsorbed N719 dye decreases with increasing density of Ti 3+ surface defects. Thus, the generation of surface defects reduces the ability of the TiO 2 surface to adsorb the dye molecules. Heating alone as pre-treatment of the TiO 2 substrates instead increases the dye adsorption, without causing detectable defects on the TiO 2 surface.

Recently, the creation of new heterogeneous catalysts using the unique electronic/geometric structures of small metal nanoclusters (NCs) has received considerable attention. However, to achieve this, it is extremely important to establish methods to remove the ligands from ligand-protected metal NCs while preventing the aggregation of metal NCs. In this study, the ligand-desorption process during calcination was followed for metal-oxide-supported 2-phenylethanethiolate-protected gold (Au) 25-atom metal NCs using five experimental techniques. The results clearly demonstrate that the ligand-desorption process consists of ligand dissociation on the surface of the metal NCs, adsorption of the generated compounds on the support and desorption of the compounds from the support, and the temperatures at which these processes occurred were elucidated. Based on the obtained knowledge, we established a method to form a metal-oxide layer on the surface of Au NCs while preventing their aggregation, thereby succeeding in creating a water-splitting photocatalyst with high activity and stability., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

A polymer made from equal masses of sulfur and canola oil was carbonised at 600 °C for 30 minutes. The resulting material exhibited improved uptake of mercury from water compared to the polymer. The carbonisation could also be done after using the polymer to clean up oil spills, which suprisingly improved mercury uptake to levels rivaling commercial carbons.

Small Ru clusters are efficient catalysts for chemical reactions such as CO hydrogenation. In this study 3-atom Ru 3 clusters were deposited onto radio frequency (RF)-deposited TiO 2 which is an inexpensive, nanoparticulate form of TiO 2 . TiO 2 substrates are notable in that they form strong metal-substrate interactions with clusters. Using temperature programmed desorption to probe Ru-CO binding sites, and X-ray photoelectron spectroscopy to provide chemical information on clusters, differences in cluster-support interactions were studied for Ru 3 deposited using both an ultra-high vacuum cluster source and chemical vapour deposition of Ru 3 (CO) 12 . The TiO 2 was treated with different Ar + sputter doses prior to cluster depositions, and SiO 2 was also used as a comparison substrate. For cluster source-deposited Ru 3 , heating to 800 K caused cluster agglomeration on SiO 2 and oxidation on non-sputtered TiO 2 . For cluster source-deposited Ru 3 on sputtered TiO 2 substrates, all Ru-CO binding sites were blocked as-deposited and it was concluded that for the binding sites to be preserved for potential catalytic benefit, sputtering of TiO 2 before cluster deposition cannot be applied. Conversely, for Ru 3 (CO) 12 on sputtered TiO 2 the clusters were protected by their ligands and Ru-CO binding sites were only blocked once the sample was heated to 723 K. The mechanism for complete blocking of CO sites on sputtered TiO 2 could not be directly determined; however, comparisons to the literature indicate that the likely reasons for blocking of the CO adsorption sites are encapsulation into the TiO x layer reduced through sputtering and also partial oxidation of the Ru clusters., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Graphene supported transition metal clusters are of great interest for potential applications, such as catalysis, due to their unique properties. In this work, a simple approach to deposit Au 101 (PPh 3 ) 21 Cl 5 (Au 101 NC) on reduced graphene oxide (rGO) via an ex situ method is presented. Reduction of graphene oxide at native pH (pH ≈ 2) to rGO was performed under aqueous hydrothermal conditions. Decoration of rGO sheets with controlled content of 5 wt% Au was accomplished using only pre-synthesised Au 101 NC and rGO as precursors and methanol as solvent. High resolution scanning transmission electron microscopy indicated that the cluster size did not change upon deposition with an average diameter of 1.4 ± 0.4 nm. It was determined that the rGO reduction method was crucial to avoid agglomeration, with rGO reduced at pH ≈ 11 resulting in agglomeration. X-ray photoelectron spectroscopy was used to confirm the deposition of Au 101 NCs and show the presence of triphenyl phosphine ligands, which together with attenuated total reflectance Fourier transform infrared spectroscopy, advocates that the deposition of Au 101 NCs onto the surface of rGO was facilitated via non-covalent interactions with the phenyl groups of the ligands. Inductively coupled plasma mass spectrometry and thermogravimetric analysis were used to determine the gold loading and both agree with a gold loading of ca . 4.8-5 wt%. The presented simple and mild strategy demonstrates that good compatibility between size-specific phosphine protected gold clusters and rGO can prevent aggregation of the metal clusters. This work contributes towards producing an agglomeration-free synthesis of size-specific ligated gold clusters on rGO that could have wide range of applications., Competing Interests: The authors have no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Unwanted growth of fouling organisms on underwater surfaces is an omnipresent challenge for the marine industry, costing billions of dollars every year in the transportation sector alone. Copper, the most widely used biocide in antifouling paints, is at the brink of a total ban in being used in antifouling coatings, as it has become an existential threat to nontargeted species due to anthropogenic copper inputs into protected waters. In the current study, using a porous and cross-linked poly(ethylene imine) structure under marine and fouling environments, available copper from natural seawater was absorbed and electrochemically released back as a potent biocide at 1.3 V vs Ag|AgCl, reducing marine growth by 94% compared to the control electrode (coupon) at 0 V. The coating can also function as an electrochemical copper sensor enabling real-time monitoring of the electrochemical uptake and release of copper ions from natural seawater. This allows tailoring of the electrochemical program to the changing marine environments, i.e., when the vessels move from high-copper-contaminated waters to coastal regions with low concentrations of copper.

Ion-surface scattering experiments can be used to measure elemental depth profiles on the angstrom scale in complex liquid mixtures. We employ NICISS (neutral impact collision ion scattering spectroscopy) to measure depth profiles of dissolved ions and solvent in liquid glycerol containing the cationic surfactant tetrahexylammonium bromide (THA + /Br - ) at 0.013 M and mixtures of NaBr + NaCl at 0.4 M total concentration. The experiments reveal that Br - outcompetes Cl - in its attraction to surface THA + , and that THA + segregates more extensively when more Br - ions are present. Intriguingly, the depths spanned by THA + , Br - , and Cl - ions generally increase with Br - bulk concentration, expanding from ∼10 to ∼25 Å for both Br - and Cl - depth profiles. This broadening likely occurs because of an increasing pileup of THA + ions in a multilayer region that spreads the halide ions over a wider depth. The experiments indicate that cationic surfactants enhance Br - and Cl - concentrations in the surface region far beyond their bulk-phase values, making solutions coated with these surfactants potentially more reactive toward gases that can oxidize the halide ions.

Stable doping of indacenodithieno[3,2- b ]thiophene (IDTT) structures enables easy color tuning and significant improvement in the charge storage capacity of electrochromic polymers, making use of their full potential as electrochromic supercapacitors and in other emerging hybrid applications. Here, the IDTT structure is copolymerized with four different donor-acceptor-donor (DAD) units, with subtle changes in their electron-donating and electron-withdrawing characters, so as to obtain four different donor-acceptor copolymers. The polymers attain important form factor requirements for electrochromic supercapacitors: desired switching between achromatic black and transparent states ( L * a * b * 45.9, -3.1, -4.2/86.7, -2.2, and -2.7 for PIDTT-TBT), high optical contrast (72% for PIDTT-TBzT), and excellent electrochemical redox stability (I red /I ox ca. 1.0 for PIDTT-EBE). Poly[indacenodithieno[3,2- b ]thiophene-2,8-diyl- alt -4,7-bis(2,3-dihydrothieno[3,4- b ][1,4]dioxin-5-yl)-2-(2-hexyldecyl)-2 H -benzo[ d ][1,2,3]triazole-7,7'-diyl] (PIDTT-EBzE) stands out as delivering simultaneously a high contrast (69%) and doping level (>100%) and specific capacitance (260 F g -1 ). This work introduces IDTT-based polymers as bifunctional electro-optical materials for potential use in color-tailored, color-indicating, and self-regulating smart energy systems., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

The photocatalytic properties of titania (TiO 2 ) have prompted research utilising its useful ability to convert solar energy into electron-hole pairs to drive novel chemistry. The aim of the present work is to examine the properties required for a synthetic method capable of producing thin TiO 2 films, with well defined, easily modifiable characteristics. Presented here is a method of synthesis of TiO 2 nanoparticulate thin films generated using RF plasma capable of homogenous depositions with known elemental composition and modifiable properties at a far lower cost than single-crystal TiO 2 . Multiple depositions regimes were examined for their effect on overall chemical composition and to minimise the unwanted contaminant, carbon, from the final film. The resulting TiO 2 films can be easily modified through heating to further induce defects and change the electronic structure, crystallinity, surface morphology and roughness of the deposited thin film., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Triplet excitons have been identified as the major obstacle to the realisation of organic laser diodes, as accumulation of triplet excitons leads to significant losses under continuous wave (CW) operation and/or electrical excitation. Here, we report the design and synthesis of a solid-state organic triplet quencher, as well as in-depth studies of its dispersion into a solution processable bis-stilbene-based laser dye. By blending the laser dye with 20 wt% of the quencher, negligible effects on the ASE thresholds, but a complete suppression of singlet-triplet annihilation (STA) and a 20-fold increase in excited-state photostability of the laser dye under CW excitation, were achieved. We used small-area OLEDs (0.2 mm 2 ) to demonstrate efficient STA suppression by the quencher in the nanosecond range, supported by simulations to provide insights into the observed STA quenching under electrical excitation. The results demonstrate excellent triplet quenching ability under both optical and electrical excitations in the nanosecond range, coupled with excellent solution processability.

Submonolayer coverages of chemically synthesised triphenylphosphine-protected Au 9 clusters on mica and TiO 2 substrates were achieved through the development of a Pulsed Nozzle Cluster Deposition (PNCD) technique under high vacuum conditions. This method offers the deposition of pre-prepared, solvated clusters directly onto substrates in a vacuum without the potential for contamination from the atmosphere. AFM and TEM were used to investigate the rate of gold cluster deposition as a function of cluster solution concentration and the number of pulses, with pulse number showing the most effective control of the final deposition conditions. TEM and XPS were used to determine that the clusters retained their unique properties through the deposition process. Methanol solvent deposited in the PNCD process has been shown to be removable through post-deposition treatments. A physical model describing the vapour behaviour and solvent evaporation in a vacuum is also developed and presented., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Metal clusters typically consist of two to a few hundred atoms and have unique properties that change with the type and number of atoms that form the cluster. Metal clusters can be generated with a precise number of atoms, and therefore have specific size, shape, and electronic structures. When metal clusters are deposited onto a substrate, their shape and electronic structure depend on the interaction with the substrate surface and thus depend on the properties of both the clusters and those of the substrate. Deposited metal clusters have discrete, individual electron energy levels that differ from the electron energy levels in the constituting individual atoms, isolated clusters, and the respective bulk material. The properties of clusters with a focus on Au and Ru, the methods to generate metal clusters, and the methods of deposition of clusters onto substrate surfaces are covered. The properties of cluster-modified surfaces are important for their application. The main application covered here is catalysis, and the methods for characterization of the cluster-modified surfaces are described., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Neutral impact ion scattering spectroscopy (NICISS) is used to measure the depth profiles of ionic surfactants, counterions, and solvent molecules on the angstrom scale. The chosen surfactants are 0.010 m tetrahexylammonium bromide (THA + /Br - ) and 0.0050 m sodium dodecyl sulfate (Na + /DS - ) in the absence and presence of 0.30 m NaBr in liquid glycerol. NICISS determines the depth profiles of the elements C, O, Na, S, and Br through the loss in energy of 5 keV He atoms that travel into and out of the liquid, which is then converted into depth. In the absence of NaBr, we find that THA + and its Br - counterion segregate together because of charge attraction, forming a narrow double layer that is 10 Å wide and 150 times more concentrated than in the bulk. With the addition of NaBr, THA + is "salted out" to the surface, increasing the interfacial Br - concentration by 3-fold and spreading the anions over a ∼30 Å depth. Added NaBr similarly increases the interfacial concentration of DS - ions and broadens their positions. Conversely, the dissolved Br - ions are significantly depleted over a depth of 0-40 Å from the surface because of charge repulsion from DS - ions within the interfacial region. These different interfacial Br - propensities correlate with previously measured gas-liquid reactivities: gaseous Cl 2 readily reacts with Br - ions in the presence of THA + but drops 70-fold in the presence of DS - , demonstrating that surfactant headgroup charge controls the reactivity of Br - through changes in its depth profile.

Tethered bilayer lipid membranes are solid supported lipid membranes, where the inner leaflet is covalently linked to the solid supported substrate through anchorlipids. These anchorlipids form a self-assembled monolayer, which serves as the basis of the membrane and also provides submembrane space. The molecular structure and composition of this monolayer has thus significant influence on the membrane structural and functional properties. The density of the self-assembled monolayer can be tailored by adding small molecules to the monolayer. Here, the structure of fully tethered and sparsely tethered monolayers, where the anchorlipid has been diluted with a small surface-active thiol, has been analyzed using neutral impact collision ion scattering spectroscopy, X-ray photoelectron spectroscopy, and metastable induced electron spectroscopy. Combination of these three techniques allowed description of the self-assembly process in detail. The monolayers have been characterized in terms of layer thickness and orientation of the lipids.

Titanium dioxide (TiO 2 ) is used to form the anode in dye sensitized solar cells (DSSCs) and is thus one of the crucial components of this type of solar cell. A large range of treatments of the titania anode before deposition of the dye have been applied to improve the performance of DSSCs among which the TiCl 4 treatment is the most frequently used treatment. The present study investigates how the TiCl 4 treatment of the TiO 2 changes the anode. For this purpose, different sample sets, nontreated, post-treated, and pre-post treated cells, were fabricated and analyzed with electron and ion scattering spectroscopy to investigate how they change the titania surface and consequently influence the cell performance. After the TiCl 4 treatment, the short circuit current density (J sc ), open-circuit voltage (V oc ), and efficiency significantly improved. An upward shift in the conduction band of the semiconductor as an effect of TiCl 4 treatment was measured using inverse photoemission spectroscopy and UV-photoelectron spectroscopy. An increase in dye adsorption due to the treatment was found through neutral impact collision ion scattering spectroscopy measurement. The change in the energy level alignment of the titania and the adsorbed dye and the increase in dye loading explain the threefold increase of power conversion of the cells.

Compact self-assembled monolayers (SAMs) of perfluorododecyl iodide (I-PFC12) of reproducible thickness (1.2 nm) are shown to form on silicon wafers. The SAMs have a high fluorine content (95%) and convey an extremely low surface energy to the silicon wafers (4.3 mN m-1), lower than previously reported in the literature for perfluorinated monolayers, and stable for over eight weeks. Shorter chain iodo-perfluorinated (I-PFC8) or bromo-perfluorinated molecules (Br-PFC10) led to less dense layers. The monolayers are stable to heating up to 60 °C, with some loss up to 150 °C. The I-PFC12 monolayer increases the work function of silicon wafers from 3.6 V to 4.4 eV, a factor that could be gainfully used in photovoltaic applications. The I-PFC12 monolayers can be transferred into patterns onto silica substrates by micro-contact printing. The NMR data and the reproducible thickness point to an upright halogen bonding interaction between the iodine in I-PFC12 and the surface oxygen on the native silica layer.

MoO 3 is widely used in polymer-based organic solar cells as an anode buffer layer because of its high workfunction and formation of a strong dipole at the MoO 3 /polymer interface facilitating charge transfer across the MoO 3 /polymer interface. In the present work, we show that exposure of the MoO 3 /polymer interface to moisture attracts water molecules to the interface via diffusion. Because of their own strong dipole, water molecules counter the dipole at the MoO 3 /polymer interface. As a consequence, the charge transfer across the MoO 3 /polymer will reduce and affect the charge transport across the interface. The outcome of this work thus suggests that it is critical to keep the MoO 3 /polymer interface moisture-free, which requires special precautions in device fabrications. The composition of the MoO 3 /P3HT:PC 61 BM interface is analyzed with X-ray photoelectron spectroscopy and the depth profiling technique, neutral impact collision ion scattering spectroscopy. The results show that the concentration of oxygen increases upon exposure but leaves the oxidation state of Mo unchanged. The valence electron spectroscopy technique shows that the dipole across the MoO 3 /P3HT:PC 61 BM interface decreases even for short-time exposure to atmosphere because of the diffusion of water molecules to the interface. The far-ranging consequences for organic electronic devices are discussed.

Increasing the power conversion efficiency of silicon (Si) photovoltaics is a key enabler for continued reductions in the cost of solar electricity. Here, we describe a two-terminal perovskite/Si tandem design that increases the Si cell's output in the simplest possible manner: by placing a perovskite cell directly on top of the Si bottom cell. The advantageous omission of a conventional interlayer eliminates both optical losses and processing steps and is enabled by the low contact resistivity attainable between n-type TiO 2 and Si, established here using atomic layer deposition. We fabricated proof-of-concept perovskite/Si tandems on both homojunction and passivating contact heterojunction Si cells to demonstrate the broad applicability of the interlayer-free concept. Stabilized efficiencies of 22.9 and 24.1% were obtained for the homojunction and passivating contact heterojunction tandems, respectively, which could be readily improved by reducing optical losses elsewhere in the device. This work highlights the potential of emerging perovskite photovoltaics to enable low-cost, high-efficiency tandem devices through straightforward integration with commercially relevant Si solar cells.

The combination of ultraviolet photoelectron spectroscopy and metastable helium induced electron spectroscopy is used to determine the density of states of the inner and outer coaxial carbon nanotubes. Ultraviolet photoelectron spectroscopy typically measures the density of states across the entire carbon nanotube, while metastable helium induced electron spectroscopy measures the density of states of the outermost layer alone. The use of double-walled carbon nanotubes in electronic devices allows for the outer wall to be functionalised whilst the inner wall remains defect free and the density of states is kept intact for electron transport. Separating the information of the inner and outer walls enables development of double-walled carbon nanotubes to be independent, such that the charge transport of the inner wall is maintained and confirmed whilst the outer wall is modified for functional purposes.

The surface composition of binary mixtures of the protic ionic liquids ethylammonium nitrate and propylammonium nitrate has been investigated using surface tension measurements and the perfectly surface sensitive method metastable induced electron spectroscopy. Given that the latter technique is sensitive only to the outermost layer, it allows for the determination of the surface fraction occupied by a given species. The piecewise linear relationship between surface fraction and surface tension found in this study can be described by a phase separation within the surface layer.

The chemical affinity of single-stranded DNA (ssDNA) to adsorb to the surface of single-walled carbon nanotubes (SWCNTs) is used for SWCNT purification, separation and in bio-devices. Despite the popularity of research on SWCNT-ssDNA conjugates, very little work has studied the removal of adsorbed ssDNA on SWCNTs. This paper reports a comprehensive study of biological, physical and chemical treatments for the removal of ssDNA from SWCNT-ssDNA suspensions. These include enzymatic cleavage, heat treatment under vacuum up to 400 °C, chemical treatments with high or low pH, oxidizing conditions, and high-ionic-strength solvents. Complimentary characterization techniques including fluorescence from a DNA-intercalating dye (YO-PRO-1) and photoelectron spectroscopy are used to exhaustively study and compare the methods investigated. Enzyme treatment is found to remove the phosphate backbone only, leaving nucleosides adsorbed to SWCNTs. Heating in inert atmosphere is ineffective at removing ssDNA. Acid, base and oxidative treatment are found to be effective for the removal of ssDNA from SWCNTs. Where possible the mechanism of desorption is described and from the findings suggestions for "best practices" are provided., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The organization of dye molecules in the dye layer adsorbed on the semiconductor substrate in dye-sensitized solar cells has been studied using a combination of theoretical methods and experimental techniques. The model system is based on the simple D-π-A dye L0, which has been chemically modified by substituting the acceptor group CN with Br (L0Br) to offer better X-ray contrast. Experimental EXAFS data based on the Br K-edge backscattering show no obvious difference between dye-sensitized titania powder and titania film samples, thus allowing model systems to be based on powder slurries. Ab initio molecular dynamic (aiMD) calculations have been performed to extract less biased information from the experimental EXASF data. Using the aiMD calculation as input, the EXAFS structural models can be generated a priori that match the experimental data. Our study shows that the L0Br dye adsorbs in the trans-L0Br configuration and that adsorption involves both a proximity to other L0Br dye molecules and the titanium atoms in the TiO 2 substrate. These results indicate direct coordination of the dye molecules to the TiO 2 surface in contrast to previous results on metal-organic dyes. The molecular coverage of L0Br on mesoporous TiO 2 was also estimated using NICIS spectroscopy. The NICISS results emphasized that the L0Br dye on nanoporous titania mainly forms monolayers with a small contribution of multilayer coverage.

A high-temperature, high-pressure, pulsed-gas sampling and detection system has been developed for testing new catalytic and photocatalytic materials for the production of solar fuels. The reactor is fitted with a sapphire window to allow the irradiation of photocatalytic samples from a lamp or solar simulator light source. The reactor has a volume of only 3.80 ml allowing for the investigation of very small quantities of a catalytic material, down to 1 mg. The stainless steel construction allows the cell to be heated to 350 °C and can withstand pressures up to 27 bar, limited only by the sapphire window. High-pressure sampling is made possible by a computer controlled pulsed valve that delivers precise gas flow, enabling catalytic reactions to be monitored across a wide range of pressures. A residual gas analyser mass spectrometer forms a part of the detection system, which is able to provide a rapid, real-time analysis of the gas composition within the photocatalytic reaction chamber. This apparatus is ideal for investigating a number of industrially relevant reactions including photocatalytic water splitting and CO 2 reduction. Initial catalytic results using Pt-doped and Ru nanoparticle-doped TiO 2 as benchmark experiments are presented.

Poly(4-vinylpyridine) (P4VP) was used as a cathode interface layer in inverted organic solar cells (OSCs) fabricated using poly[2,3-bis(3-octyloxyphenyl)quinoxaline-5,8-diyl-alt-thiophene-2,5-diyl] (TQ1) and PC 71 BM (phenyl C 71 butyric acid methyl ester) as the donor and acceptor materials, respectively. We successfully demonstrate that the work function of underlying indium tin oxide (ITO) electrode can be significantly reduced by ∼0.7 eV, after modification of the surface with a thin film of P4VP. Photoconversion efficiency of 4.7% was achieved from OSCs incorporating P4VP interface layer between the ITO and bulk heterojunction (BHJ). Thin P4VP layer, when used to modify ZnO electron transport layer in inverted OSCs, reduced the ZnO work function from 3.7 to 3.4 eV, which resulted in a noteworthy increase in open-circuit voltage from 840 to 890 mV. On simultaneous modification of ZnO with P4VP and optimization of the BHJ morphology by using solvent additive chloronapthalene, photoconversion efficiency of OSCs was significantly increased from 4.6% to 6.3%. The enhanced device parameters are also attributed to an energetically favorable material stratification, as a result of an enrichment of PC 71 BM toward the P4VP interface.

A robust solution phase ligand exchange system for lead sulfide (PbS) quantum dots (QDs) in the presence of Pb-thiolate ligands is presented that can better preserve the excitonic absorption and emission features as compared to the conventional ligands. The photoluminescence after ligand exchange of PbS QDs with Pb-thiolate ligand is preserved up to 78% of the original oleate capped PbS QDs., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Triphenylphosphine ligand-protected Au9 clusters deposited onto titania nanosheets show three different atomic configurations as observed by scanning transmission electron microscopy. The configurations observed are a 3-dimensional structure, corresponding to the previously proposed Au9 core of the clusters, and two pseudo-2-dimensional (pseudo-2D) structures, newly found by this work. With the help of density functional theory (DFT) calculations, the observed pseudo-2D structures are attributed to the low energy, de-ligated structures formed through interaction with the substrate. The combination of scanning transmission electron microscopy with DFT calculations thus allows identifying whether or not the deposited Au9 clusters have been de-ligated in the deposition process.