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Wide band-gap organic solar cells are gaining interest due to their applications in emergent light-harvesting technologies such as underwater photovoltaics, multi-junction solar cells, or indoor photovoltaics. In this work, a combinatorial screening approach is used to explore binary combinations of three wide band-gap donors (PTQ10, PM6, and D18) and three wide band-gap acceptors (PMI-FF-PMI, O-IDFBR, and IO-4Cl) deposited from solution in two solvents (CB and CF). In total, 18 combinations are blade-coated with active layers exhibiting a thickness gradient generating solar cells with 12 different thicknesses. PTQ10:IO-4Cl and PTQ10:O-IDFBR are the most efficient blends with efficiencies of 7.31% and 6.87%, respectively. The voltage loss analysis shows that PTQ10-based devices exhibit the lowest non-radiative voltage losses, whereby the PTQ10:O-IDFBR combination has the lowest voltage loss of all studied blends, with a remarkably high open-circuit voltage (Voc) of 1.35 V. Due to their high performance and Voc, PTQ10:O-IDFBR devices were also studied for indoor light harvesting, achieving an efficiency of 22.6% and a Voc of 1.21 V under 560 lux indoor illumination. To the best of our knowledge, this indoor Voc value is the highest achieved in the field of indoor organic photovoltaics. [ABSTRACT FROM AUTHOR]

Low‐bandgap nonfullerene acceptors (NFAs) offer a unique potential for photovoltaic (PV) applications, such as transparent PV and agrivoltaics. Evaluating each new PV system to achieve the optimum thickness, microstructure, and device performance is, however, a complex multiparametric challenge with large time and resource requirements. Herein, the PV potential of low‐bandgap donor and NFA materials by combining high‐throughput screening and statistical methods is evaluated. The use of thickness gradients (20–600 nm) facilitates the fabrication of more than 2000 doctor‐bladed devices from 24 different low‐bandgap blend combinations. The corresponding power conversion efficiencies varies significantly, from 0.06% to 10.45% across materials and thicknesses. The self‐consistency of the large dataset allows to perform a parameter sensitivity study as well as parameter correlation analysis. These reveal that the choice of materials and energy alignment‐related features (i.e., electron affinity offset, ionization energy offset, bandgap, and energy loss) has the largest influence on final device performance, while processing conditions appear less important for the final efficiencies. Our study demonstrates that high‐throughput experimentation is a perfect match for correlation analyses in order to gain a statistically meaningful understanding of these systems, potentially accelerating the discovery of new materials. [ABSTRACT FROM AUTHOR]

We report a multi-purpose spectrum-on-demand light source (SOLS), conceived primarily but not exclusively for the multiple and advanced characterization of photovoltaic (PV) materials and devices. The apparatus is a spectral shaper illumination device, providing a tunable and spectrally shaped light beam produced by modulating the intensity and/or wavelength range of a primary light source. SOLS stands out from the state of the art because it produces almost any spectrum on demand and delivers two types of output: a spectrally shaped and spatially homogeneous beam over its cross section for areal illumination or a spatially and spectrally split beam into its wavelength components, a unique capability suited to characterize lateral-tandem (Rainbow) solar cells. The tuneability from broadband to narrowband illumination enables two characterization devices into one, namely, a solar simulator for the determination of the power conversion efficiency and an external quantum efficiency measuring system. We expect the SOLS setup to accelerate material screening, enabling the discovery and optimization of novel multi-component materials and devices, in particular for emergent PV technologies like organic, metal halide perovskites, or multi-junction geometries, as well as novel PV applications such as indoors, building integrated, or agrivoltaics, among others. [ABSTRACT FROM AUTHOR]

In this study, nanocrystals of antiferromagnetic Cr2O3 are shown via Raman spectroscopy to display peculiar lattice dynamics in terms of phonon softening and the occurrence of an exceptionally strong spin‐phonon coupling. This effect, which is observed to persist well above the onset of the antiferromagnetic ordering temperature, is ascribed to locally correlated spin fluctuations due to the modulation of the magnetic exchange interactions as the chromium atoms oscillate about their equilibrium position. It is found that the spin‐phonon coupling strength is governed by the competing antiferromagnetic and ferromagnetic interactions, where changes in the surface spin configuration can also play a crucial role. Overall, this work proves the size dependence of the interplay between the crystalline and magnetic structures in 3D antiferromagnets varying the surface‐to‐volume ratio and helps establish the fundamentals for a spin‐phonon coupling engineering at the nanoscale via a simple route in a very stable and easy to synthesize material. More importantly, it demonstrates the possibility of coupling phononic excitations with the magnetization dynamics at room temperature, offering a highly prospective nanomaterial for the design of novel magnonic devices. [ABSTRACT FROM AUTHOR]

The exceptional optoelectronic properties of metal halide perovskites (MHPs) are presumed to arise, at least in part, from the peculiar interplay between the inorganic metal-halide sublattice and the atomic or molecular cations enclosed in the cage voids. The latter can exhibit a roto-translative dynamics, which is shown here to be at the origin of the structural behavior of MHPs as a function of temperature, pressure and composition. The application of high hydrostatic pressure allows for unraveling the nature of the interaction between both sublattices, characterized by the simultaneous action of hydrogen bonding and steric hindrance. In particular, we find that under the conditions of unleashed cation dynamics, the key factor that determines the structural stability of MHPs is the repulsive steric interaction rather than hydrogen bonding. Taking as example the results from pressure and temperature-dependent photoluminescence and Raman experiments on MAPbBr 3 but also considering the pertinent MHP literature, we provide a general picture about the relationship between the crystal structure and the presence or absence of cationic dynamic disorder. The reason for the structural sequences observed in MHPs with increasing temperature, pressure, A-site cation size or decreasing halide ionic radius is found principally in the strengthening of the dynamic steric interaction with the increase of the dynamic disorder. In this way, we have deepened our fundamental understanding of MHPs; knowledge that could be coined to improve performance in future optoelectronic devices based on this promising class of semiconductors. [ABSTRACT FROM AUTHOR]

We developed a novel contactless frequency-domain thermoreflectance approach to study thermal transport, which is particularly convenient when thermally anisotropic materials are considered. The method is based on a line-shaped heater geometry, produced with a holographic diffractive optical element, instead of using a spot heater as in conventional thermoreflectance. The heater geometry is similar to the one used in the 3-omega method, however, keeping all the technical advantages offered by non-contact methodologies. The present method is especially suitable to determine all the elements of the thermal conductivity tensor, which is experimentally achieved by simply rotating the sample with respect to the line-shaped optical heater. We provide the mathematical solution of the heat equation for the cases of anisotropic substrates, thin films, and multilayer systems. This methodology allows an accurate determination of the thermal conductivity and does not require complex modeling or intensive computational efforts to process the experimental data, i.e., the thermal conductivity is obtained through a simple linear fit ("slope method"), in a similar fashion to the 3-omega method. We demonstrate the potential of this approach by studying isotropic and anisotropic materials in a wide range of thermal conductivities. In particular, we have studied the following inorganic and organic systems: (i) glass, Si, and Ge substrates (isotropic), (ii) β-Ga2O3 and a Kapton substrate (anisotropic), and (iii) a 285 nm thick SiO2 thin film deposited on a Si substrate. The accuracy in the determination of the thermal conductivity is estimated as ≈5%, whereas the temperature uncertainty is ΔT ≈ 3 mK. [ABSTRACT FROM AUTHOR]

The high defect tolerance of metal halide perovskites, in terms of their exceptional optoelectronic properties, is assumed to be due to the very fact that most native point defects are shallow, which does not contribute to the non‐radiative recombination of free carriers. Here, a systematic study is presented, which concerns the evolution of shallow‐defect signatures observed at low temperatures in the photoluminescence (PL) spectra of mixed organic‐cation lead iodide perovskite single crystals (FAxMA1−xPbI3, where MA stands for methylammonium and FA for formamidinium). Below ≈100 K, a number of peak‐like features become clearly apparent in the PL spectra at energies lower than the strong free‐exciton emission, which are related to the radiative recombination of bound exciton complexes associated with native shallow defects (donors and/or acceptors). Based on state‐of‐the‐art ab initio calculations, a tentative assignment is provided for all PL features to different shallow‐defects (Pb, I, and MA vacancies as well as I interstitials) typically present in hybrid perovskites. The defect‐related signatures exhibit a clear trend regarding the mixed‐crystal composition, indicating that the material becomes less prone to defect formation with increasing FA content. [ABSTRACT FROM AUTHOR]

Coupling thermoelectrics (TE) with photovoltaics (PV) has emerged as an approach to solid-state solar harvesting, directly converting light and infrared heat into electricity. In this work, we compare PV-TE hybrid devices based on organic semiconductors in three different geometries: a reflection geometry, a non-contact transmission geometry, and a contact transmission geometry. The temperature rises of films of common organic thermoelectric materials, including poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), single-walled carbon nanotubes (swCNT), and poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT), were measured in configurations representative of the proposed geometries. Because organic semiconductors possess broadband light absorption and low thermal conductivities, a significant rise in temperature was observed under illumination for all geometries. We find, however, that the best configuration is, in fact, the transmission contact mode because it sums two effects. Operating under 1 sun illumination, the temperature of a commercial organic PV module increased by ≈30 K, which leads to an enhancement in OPV performance compared to room temperature. After attaching a thermoelectric to the OPV module, losses from convection are reduced, and the OPV module heats up even more, further increasing its efficiency while additionally enabling thermoelectric generation. Finally, we calculate theoretical thermoelectric efficiencies for the materials and their respective power densities. [ABSTRACT FROM AUTHOR]

Organic-inorganic hybrid perovskites have the generic formula ABX 3 , where X denotes a halide anion and A and B stand for an organic and a metal cation, respectively. These hybrid compounds are semiconductors with highly interesting and tunable properties. They are the subject of intense research for several applications, mainly in solar cells but also as light-emitting diodes and lasers. Tunability of the optical properties may be accomplished by site-substituted solid solutions in A, B, or X sites. In particular, some mixed-cation systems show increased stability for these applications. In this work, the authors report on the variation of the optical constants in mixed A-site cation methylammonium/formamidinium (MA/FA) lead iodide perovskites FA x MA 1 − x PbI 3 evaluated by spectroscopic ellipsometry in single crystal samples. The two main polymorphs of FAPbI 3 are measured. The study is complemented by photoluminescence measurements to gain a better insight into observed spectroscopic features related to the electronic interband transitions of the crystals and their structural integrity. The main result is a continuous variation of the pseudocubic perovskite band structure of the solid solutions between the two end compounds MAPbI 3 and α -FAPbI 3. [ABSTRACT FROM AUTHOR]

The choice of a reflective optical coating or filter material has to be adapted to the intended field of application. This is mainly determined by the required photon energy range or by the required reflection angle. Among various materials, nickel and rhodium are common materials used as reflective coatings for (soft) X‐ray mirrors. Similarly, aluminium is one of the most commonly used materials for extreme ultraviolet and soft X‐ray transmission filters. However, both of these types of optics are subject to carbon contamination, which can be increasingly problematic for the operation of the high‐performance free‐electron laser and synchrotron beamlines. As an attempt to remove this type of contamination, an inductively coupled plasma source has been used in conjunction with N2/O2/H2 and N2/H2 feedstock gas plasmas. Results from the chemical surface analysis of the above materials before and after plasma treatment using X‐ray photoelectron spectroscopy are reported. It is concluded that a favorable combination of an N2/H2 plasma feedstock gas mixture leads to the best chemical surface preservation of Ni, Rh and Al while removing the carbon contamination. However, this feedstock gas mixture does not remove C contamination as rapidly as, for example, an N2/O2/H2 plasma which induces the surface formation of NiO and NiOOH in Ni and RhOOH in Rh foils. As an applied case, the successful carbon removal from ultrathin Al filters previously used at the FERMI FEL1 using an N2/H2 plasma is demonstrated. A chemically neutral low‐pressure RF plasma cleaning technique for Ni, Rh and Al reflective coatings is presented. The successful carbon contamination cleaning of thin Al filters (100 nm thickness) for FEL and EUV applications is also demonstrated. [ABSTRACT FROM AUTHOR]

The process of crystallization of lead halide perovskites by industrially relevant techniques involving non-toxic solvents is not understood completely and needs improvement. To this date, devices with the highest efficiency are prepared by deposition of the perovskite layer using non-scalable techniques, toxic solvents and/or require additional processing steps. In this work, we show that perovskite solar cells can be obtained efficiently in one step by doctor blade. The perovskite film is formed under a supersaturation regime from non-toxic solvents following spherulitic growth. This method results in highly crystalline perovskite films with preferential crystal orientation. Co-local photoluminescence and light-beam induced current experiments show that the generated chemical defects are confined at the boundary of spherulites and do not have a negative effect on the extracted photocurrent. Strikingly, spherulite formation, rather than being detrimental, could lead to better photovoltaic performance in hybrid perovskite films. This is further confirmed in the photovoltaic devices, which were fabricated using non-toxic solvents by doctor blade process, with record efficiencies of 18.0% for MAPbI3 (MA = methyl ammonium). Moreover, devices with large area (1.53 cm2) fabricated using doctor blade show remarkable efficiencies (14.2%) reinforcing the viability of this solar technology towards industrialization. [ABSTRACT FROM AUTHOR]

As contamination and environmental degradation increase, there is a huge demand for new eco-friendly materials. Despite its use for thousands of years, cellulose and its derivatives have gained renewed interest as favourable alternatives to conventional plastics, due to their abundance and lower environmental impact. Here, we report the fabrication of photonic and plasmonic structures by moulding hydroxypropyl cellulose into submicrometric periodic lattices, using soft lithography. This is an alternative way to achieve structural colour in this material, which is usually obtained by exploiting its chiral nematic phase. Cellulose-based photonic crystals are biocompatible and can be dissolved in water or not depending on the derivative employed. Patterned cellulose membranes exhibit tunable colours and may be used to boost the photoluminescence of a host organic dye. Furthermore, we show how metal coating these cellulose photonic architectures leads to plasmonic crystals with excellent optical properties acting as disposable surface-enhanced Raman spectroscopy substrates. Biodegradable cellulose-based photonic and plasmonic architectures are fabricated via soft nanoimprinting lithography, and are used for structural colour generation, photoluminescence enhancement and as disposable surface-enhanced Raman scattering substrates. [ABSTRACT FROM AUTHOR]

Abstract: Carbonaceous materials are extensively applied to the development of electrochemical devices for electroanalysis, energy conversion, and storage or electrocatalysis because of their rather unique features that include high chemical stability, low cost, and wide potential window. Furthermore, they are processed into thick or thin‐film structures onto different substrates for producing electrode devices whose widespread use, however, is hampered by the film composition and the poor mechanical stability. Here the application of carbon/silica composites is shown to produce miniaturized thin‐film electrodes, which stand out for their robustness and can thus be used repeatedly for electrochemical analysis. Resorcinol‐formaldehyde/(3‐aminopropyl)triethoxysilane sol–gel films on silicon substrates are subjected to several processes that combine lithography, etching, and pyrolysis steps to yield carbon/silica thin‐film electrodes, at wafer scale. The presence of silica in the electrode material promotes strong interfacial adhesion to the substrate, dramatically increasing the number of measurements a single electrode can withstand without loss of performance. The thorough electroanalytical characterization by cyclic voltammetry in solutions containing representative redox species reveals an electrode performance comparable to that of glassy carbon for outer‐sphere redox processes. In addition, the modification of the electrode surface with metal nanoparticles allows for the sensitive detection of heavy metal ion pollutants. [ABSTRACT FROM AUTHOR]

We report a methodology based on Raman spectroscopy that enables the non-invasive and fast quantitative determination of local thickness and composition in thin films (from a few monolayers to hundreds of nm) of one or more components. We apply our methodology to blends of organic conjugated materials relevant in the field of organic photovoltaics. As a first step, we exploit the transfer-matrix formalism to describe the Raman process in thin films including reabsorption and interference effects of the incoming and scattered electric fields. This allows determining the effective solid-state Raman cross-section of each material by studying the dependence of the Raman intensity on film thickness. These effective cross sections are then used to estimate the local thickness and composition in a series of polymer:fullerene blends. We find that the model is accurate within ±10 nm in thickness and ±5 vol% in composition provided that (i) the film thickness is kept below the thickness corresponding to the first maximum of the calculated Raman intensity oscillation; (ii) the materials making up the blend show close enough effective Raman cross-sections; and (iii) the degree of order attained by the conjugated polymer in the blend is similar to that achieved when cast alone. Our methodology opens the possibility of making quantitative maps of composition and thickness over large areas (from microns to centimetres squared) with diffraction-limited resolution and in any multi-component system based thin film technology. [ABSTRACT FROM AUTHOR]

We present Raman and terahertz absorbance spectra of methylammonium lead halide single crystals (MAPbX3, X = I, Br, Cl) at temperatures between 80 and 370 K. These results show good agreement with density-functional-theory phonon calculations. Comparison of experimental spectra and calculated vibrational modes enables confident assignment of most of the vibrational features between 50 and 3500 cm−1. Reorientation of the methylammonium cations, unlocked in their cavities at the orthorhombic-to-tetragonal phase transition, plays a key role in shaping the vibrational spectra of the different compounds. Calculations show that these dynamic effects split Raman peaks and create more structure than predicted from the independent harmonic modes. This explains the presence of extra peaks in the experimental spectra that have been a source of confusion in earlier studies. We discuss singular features, in particular the torsional vibration of the C–N axis, which is the only molecular mode that is strongly influenced by the size of the lattice. From analysis of the spectral linewidths, we find that MAPbI3 shows exceptionally short phonon lifetimes, which can be linked to low lattice thermal conductivity. We show that optical rather than acoustic phonon scattering is likely to prevail at room temperature in these materials. [ABSTRACT FROM AUTHOR]

The solid solution Sr2−xLaxSiO4−xNx (0 ≥x≥ 1), obtained by concomitant substitution of Sr2+ by La3+ and O2− by N3− in Sr2SiO4, has been prepared by solid state reaction at 1500 °C in N2/H2 of mixtures of SrO, La2O3, SiO2 and Si3N4. Synchrotron radiation X-ray diffraction studies show a transition from the monoclinic P21/n symmetry of β-Sr2SiO4 to orthorhombic Pmnbα′,β-K2SO4 type phase for x≥ 0.2. The α′ phase is stabilized as a consequence of the increase in bond valence of the cations induced by nitriding. The activation with Eu2+ and Ce3+ of Sr2−xLaxSiO4−xNx produces luminescent materials with broad emission bands centered up to 650 nm under excitation at 405 nm. The emission wavelengths are tuned by La/N contents in a wide range with emission colours changing from yellow (x = 0.2) to orange-red (x = 1) for Eu2+ phosphors and from blue-green (x = 0.2) to orange-yellow (x = 1) in Ce3+ samples. [ABSTRACT FROM AUTHOR]

The new compounds LaSrSiO3N and LaBaSiO3N activated with Eu2+ are orange-red light-emitting luminescent materials under excitation in the UV-blue range. They represent the first examples of stoichiometric alkaline earth oxynitridosilicates with a β-K2SO4 structure. The isostructural compound LaEuSiO3N is ferromagnetic with a Curie temperature of 3 K and also shows red luminescence (λmax = 705 nm) under excitation at 405 nm. [ABSTRACT FROM AUTHOR]

The microstructure of blend films of conjugated polymer and fullerene, especially the degree of mixing and crystallization, impacts the performance of organic photovoltaic devices considerably. Mixing and crystallization affect device performance in different ways. These phenomena are not easy to screen using traditional methods such as imaging. In this paper, the amorphous regiorandom poly(3-hexylthiophene) is blended with the potentially crystalline fullerene [6,6]-phenyl-C61-butyric acid methyl ester PCBM and the amorphous bis-adduct. First, the degree of mixing of polymer: fullerene blends is evaluated using UV-Vis absorption, steady-state and ultra-fast photoluminescence spectroscopy. The blue-shift of the polymer emission and absorption onset are used in combination with the saturation of the polymer emission decay time upon fullerene addition in order to infer the onset of aggregation of the blends. Second, the crystallinity of the fullerene is probed using variable angle spectroscopic ellipsometry (VASE), electroluminescence and photoluminescence spectroscopy. It is shown that the red-shift of charge transfer emission in the case of PCBM based blends cannot be explained solely by a variation of optical dielectric constant as probed by VASE. A combination of optical spectroscopy techniques, therefore, allows to probe the degree of mixing and can also distinguish between aggregation and crystallization of fullerenes. [ABSTRACT FROM AUTHOR]

Correction for 'Comparing different geometries for photovoltaic-thermoelectric hybrid devices based on organics' by José P. Jurado et al., J. Mater. Chem. C, 2021, 9, 2123–2132, DOI: 10.1039/D0TC05067A. [ABSTRACT FROM AUTHOR]

We report on an organic photodiode configuration based on a donor/acceptor bilayer with opposed complementary thickness gradients. We rely on the strong dependence of the optical field on thickness to achieve spatially dependent spectral responses, a proof-of-concept for position sensitive detection. Ratiometric photocurrent values at two wavelengths allow for position determination independently of the light intensity with a spatial resolution below 600 μm. [ABSTRACT FROM AUTHOR]