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The solid-state optical gain characteristics of a spiroanthracenefluorene polymer, namely, poly(9-spiro(10,10-bis(2-ethylhexyl)-10H-anthracene)fluorene (PEHSAF), specifically designed for thermal stability is reported. The PEHSAF stimulated emission characteristics are demonstrated to be thermally stable in vacuo for temperatures up to 250 degree Celsius.

We report the solid-state optical gain characteristics of a spiroanthracenefluorene polymer, namely, poly(9-spiro(10,10-bis(2-ethylhexyl)-10H-anthracene)fluorene) (PEHSAF), specifically designed for thermal stability. An efficient stimulated emission occurs at λ=445 nm under amplified spontaneous emission conditions for asymmetric slab waveguide structures. The modal gain and propagation loss coefficients were found to be g<=38 cm-1 and α=0.8 cm-1, respectively. The PEHSAF stimulated emission characteristics are shown to be thermally stable in vacuo for temperatures up to 250 °C. Surface-emitting distributed feedback lasers have been fabricated by spin-coating PEHSAF onto one-dimensional grating structures. The lasers operate in the blue spectral region and exhibit low oscillation thresholds (>=18 nJ) and relatively high slope efficiencies (<=5%). Varying the PEHSAF film thickness allows the tuning of the emission wavelength within a 16 nm window. [ABSTRACT FROM AUTHOR]

We present a detailed structural and surface-enhanced Raman scattering (SERS) study of poly(allylamine) modified with Os(byp)2ClPyCHO (PAH-Os) and gold nanoparticles self-assembled multilayers [PAH-Os+(Au-nanoparticles/PAH-Os)n, n=1 and 5]. Atomic force microscopy and variable-angle spectroscopic ellipsometry measurements indicate that the first nanoparticle layer grows homogenously by partially covering the substrate without clustering. Analyzing the sample thickness and roughness we infer that the growth process advances thereafter by filling with nanoparticles the interstitial spaces between the previously adsorbed nanoparticles. After five immersion steps the multilayers reach a more compact structure. The interaction between plasmons of near-gold nanoparticles provides a new optical absorption around 650 nm which, in addition, allows a more effective SERS process in that spectral region than at the single-plasmon resonance (∼530 nm). We compare the electronic resonance Raman and SERS amplification mechanisms in these self-assembled multilayers analyzing Raman resonance scans and Raman intensity micromaps. As a function of nanoparticle coverage we observe large changes in the Raman intensity scans, with maxima that shift from the electronic transitions, to the plasmon resonance, and finally to the coupled-plasmon absorption. The Raman micromaps, on the other hand, evidence huge intensity inhomogeneities which we relate to “hot spots.” Numerical discrete dipole approximation calculations including the interaction between gold nanoparticles are presented, providing a qualitative model for the coupled-plasmon absorption and redshifted Raman hot spots in these samples. [ABSTRACT FROM AUTHOR]

We report on the investigation by spectroscopic ellipsometry of films containing Cd 1 − x Hg x Te alloy quantum dots (QDs). The alloy QDs were fabricated from colloidal CdTe QDs grown by an aqueous synthesis process followed by an ion-exchange step in which Hg 2+ ions progressively replace Cd 2+ . For ellipsometric studies, several films were prepared on glass substrates using layer-by-layer (LBL) deposition. The contribution of the QDs to the measured ellipsometric spectra is extracted from a multi-sample, transmission and multi- angle-of-incidence ellipsometric data analysis fitted using standard multilayer and effective medium models that include surface roughness effects, modeled by an effective medium approximation. The relationship of the dielectric function of the QDs retrieved from these studies to that of the corresponding II–VI bulk material counterparts is presented and discussed. [ABSTRACT FROM AUTHOR]

Glycol sidechains are often used to enhance the performance of organic photoconversion and electrochemical devices. Herein, we study their effects on electronic states and electronic properties. We find that polymer glycolation not only induces more disordered packing, but also results in a higher reorganisation energy due to more localised π-electron density. Transient absorption spectroscopy and femtosecond stimulated Raman spectroscopy are utilised to monitor the structural relaxation dynamics coupled to the excited state formation upon photoexcitation. Singlet excitons are initially formed, followed by polaron pair formation. The associated structural relaxation slows down in glycolated polymers (5 ps vs. 1.25 ps for alkylated), consistent with larger reorganisation energy. This slower vibrational relaxation is found to drive ultrafast formation of the polaron pair state (5 ps vs. 10 ps for alkylated). These results provide key experimental evidence demonstrating the impact of molecular structure on electronic state formation driven by strong vibrational coupling., (© 2024. The Author(s).)

Chemical doping of organic semiconductors is an essential enabler for applications in electronic and energy-conversion devices such as thermoelectrics. Here, Lewis-paired complexes are advanced as high-performance dopants that address all the principal drawbacks of conventional dopants in terms of limited electrical conductivity, thermal stability, and generality. The study focuses on the Lewis acid B(C 6 F 5 ) 3 (BCF) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ) bearing Lewis-basic -CN groups. Due to its high electron affinity, BCF:F 4 TCNQ dopes an exceptionally wide range of organic semiconductors, over 20 of which are investigated. Complex activation and microstructure control lead to conductivities for poly(3-hexylthiophene) (P3HT) exceeding 300 and 900 S cm -1 for isotropic and chain-oriented films, respectively, resulting in a 10 to 50 times larger thermoelectric power factor compared to those obtained with neat dopants. Moreover, BCF:F 4 TCNQ-doped P3HT exhibits a 3-fold higher thermal dedoping activation energy compared to that obtained with neat dopants and at least a factor of 10 better operational stability., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Simple synthetic routes, high active layer thickness tolerance as well as stable organic solar cells are relentlessly pursued as key enabling traits for the upscaling of organic photovoltaics. Here, the potential to address these issues by tuning donor polymer molecular weight is investigated. Specifically, the focus is on PTQ10, a polymer with low synthetic complexity, with number average molecular weights of 2.4, 6.2, 16.8, 52.9, and 54.4 kDa, in combination with three different non-fullerene acceptors, namely Y6, Y12, and IDIC. Molecular weight, indeed, unlocks a threefold increase in power conversion efficiency for these blends. Importantly, efficiencies above 10% for blade coated devices with thicknesses between 200 and 350 nm for blends incorporating high molecular weight donor are shown. Spectroscopic, GIWAXS and charge carrier mobility data suggest that the strong photocurrent improvement with molecular weight is related to both, improved electronic transport and polymer contribution to exciton generation. Moreover, it is demonstrated that solar cells based on high molecular weight PTQ10 are more thermally stable due to a higher glass transition temperature, thus also improving device stability., (© 2024 The Authors. Small published by Wiley‐VCH GmbH.)

While multi-junction geometries have the potential to boost the efficiency of organic solar cells, the experimental gains yet obtained are still very modest. This work proposes an alternative spectral splitting device concept in which various individual semiconducting junctions with cascading bandgaps are laid side by side, thus the name RAINBOW. Each lateral sub-cell receives a fraction of the spectrum that closely matches the main absorption band of the given semiconductor. Here, simulations are used to identify the important material and device properties of each RAINBOW sub-cell. Using the resulting design rules, three systems are selected, with narrow, medium, and wide effective bandgaps, and their potential as sub-cells in this geometry is experimentally investigated. With the aid of a custom-built setup that generates spectrally spread sunlight on demand, the simulations are experimentally validated, showing that this geometry can lead to a reduction in thermalization losses and an improvement in light harvesting, which results in a relative improvement in efficiency of 46.6% with respect to the best sub-cell. Finally, a working proof-of-concept monolithic device consisting of two sub-cells deposited from solution on the same substrate is fabricated, thus demonstrating the feasibility and the potential of the RAINBOW solar cell concept., (© 2023 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

In order for organic thermoelectrics to successfully establish their own niche as energy-harvesting materials, they must reach several crucial milestones, including high performance, long-term stability, and scalability. Performance and stability are currently being actively studied, whereas demonstrations of large-scale compatibility are far more limited and for carbon nanotubes (CNTs) are still missing. The scalability challenge includes material-related economic considerations as well as the availability of fast deposition methods that produce large-scale films that simultaneously satisfy the thickness constraints required for thermoelectric modules. Here we report on true solutions of CNTs that form gels upon air exposure, which can then be dried into micron-thick films. The CNT ink can be extruded using a slot-shaped nozzle into a continuous film (more than half a meter in the present paper) and patterned into alternating n- and p-type components, which are then folded to obtain the finished thermoelectric module. Starting from a given n-type film, differentiation between the n and p components is achieved by a simple postprocessing step that involves a partial oxidation reaction and neutralization of the dopant. The presented method allows the thermoelectric legs to seamlessly interconnect along the continuous film, thus avoiding the need for metal electrodes, and, most importantly, it is compatible with large-scale printing processes. The resulting thermoelectric legs retain 80% of their power factor after 100 days in air and about 30% after 300 days. Using the proposed methodology, we fabricate two thermoelectric modules of 4 and 10 legs that can produce maximum power outputs of 1 and 2.4 μW, respectively, at a temperature difference Δ T of 46 K., Competing Interests: The authors declare the following competing financial interest(s): A patent on this work has been filed., (© 2024 The Authors. Published by American Chemical Society.)

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., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Conjugated polymers with oligoether side chains make up a promising class of thermoelectric materials. In this work, the impact of the side-chain length on the thermoelectric and mechanical properties of polythiophenes is investigated. Polymers with tri-, tetra-, or hexaethylene glycol side chains are compared, and the shortest length is found to result in thin films with the highest degree of order upon doping with the p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ). As a result, a stiff material with an electrical conductivity of up to 830 ± 15 S cm -1 is obtained, resulting in a thermoelectric power factor of about 21 μW m -1 K -2 in the case of as-cast films. Aging at ambient conditions results in an initial decrease in thermoelectric properties but then yields a highly stable performance for at least 3 months, with values of about 200 S cm -1 and 5 μW m -1 K -2 . Evidently, identification of the optimal side-chain length is an important criterion for the design of conjugated polymers for organic thermoelectrics., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The low endogenous regenerative capacity of the heart, added to the prevalence of cardiovascular diseases, triggered the advent of cardiac tissue engineering in the last decades. The myocardial niche plays a critical role in directing the function and fate of cardiomyocytes; therefore, engineering a biomimetic scaffold holds excellent promise. We produced an electroconductive cardiac patch of bacterial nanocellulose (BC) with polypyrrole nanoparticles (Ppy NPs) to mimic the natural myocardial microenvironment. BC offers a 3D interconnected fiber structure with high flexibility, which is ideal for hosting Ppy nanoparticles. BC-Ppy composites were produced by decorating the network of BC fibers (65 ± 12 nm) with conductive Ppy nanoparticles (83 ± 8 nm). Ppy NPs effectively augment the conductivity, surface roughness, and thickness of BC composites despite reducing scaffolds' transparency. BC-Ppy composites were flexible (up to 10 mM Ppy), maintained their intricate 3D extracellular matrix-like mesh structure in all Ppy concentrations tested, and displayed electrical conductivities in the range of native cardiac tissue. Furthermore, these materials exhibit tensile strength, surface roughness, and wettability values appropriate for their final use as cardiac patches. In vitro experiments with cardiac fibroblasts and H9c2 cells confirmed the exceptional biocompatibility of BC-Ppy composites. BC-Ppy scaffolds improved cell viability and attachment, promoting a desirable cardiomyoblast morphology. Biochemical analyses revealed that H9c2 cells showed different cardiomyocyte phenotypes and distinct levels of maturity depending on the amount of Ppy in the substrate used. Specifically, the employment of BC-Ppy composites drives partial H9c2 differentiation toward a cardiomyocyte-like phenotype. The scaffolds increase the expression of functional cardiac markers in H9c2 cells, indicative of a higher differentiation efficiency, which is not observed with plain BC. Our results highlight the remarkable potential use of BC-Ppy scaffolds as a cardiac patch in tissue regenerative therapies.

Understanding the complex crystallization process of semiconducting polymers is key for the advance of organic electronic technologies as the optoelectronic properties of these materials are intimately connected to their solid-state microstructure. These polymers often have semirigid backbones and flexible side chains, which results in a strong tendency to organize/order in the liquid state. Therefore, crystallization of these materials frequently occurs from liquid states that exhibit-at least partial-molecular order. However, the impact of the preexisting molecular order on the crystallization process of semiconducting polymers- indeed, of any polymer-remained hitherto unknown. This study uses fast scanning calorimetry (FSC) to probe the crystallization kinetics of poly(9,9-di- n -octylfluorenyl-2,7-diyl (PFO) from both an isotropic disordered melt state ( ISO state ) and a liquid-crystalline ordered state ( NEM state ). Our results demonstrate that the preexisting molecular order has a profound impact on the crystallization of PFO. More specifically, it favors the formation of effective crystal nucleation centers, speeding up the crystallization kinetics at the early stages of phase transformation. However, samples crystallized from the NEM state require longer times to reach full crystallization (during the secondary crystallization stage) compared to those crystallized from the ISO state , likely suggesting that the preexisting molecular order slows down the advance in the latest stages of the crystallization, that is, those governed by molecular diffusion. The fitting of the data with the Avrami model reveals different crystallization mechanisms, which ultimately result in a distinct semicrystalline morphology and photoluminescence properties. Therefore, this work highlights the importance of understanding the interrelationships between processing, structure, and properties of polymer semiconductors and opens the door for performing fundamental investigations via newly developed FSC methodologies of such materials that otherwise are not possible with conventional techniques., Competing Interests: The authors declare no competing financial interest., (© 2022 American Chemical Society.)

Non-fullerene acceptors (NFAs) are excellent light harvesters, yet the origin of their high optical extinction is not well understood. In this work, we investigate the absorption strength of NFAs by building a database of time-dependent density functional theory (TDDFT) calculations of ∼500 π-conjugated molecules. The calculations are first validated by comparison with experimental measurements in solution and solid state using common fullerene and non-fullerene acceptors. We find that the molar extinction coefficient ( ε d,max ) shows reasonable agreement between calculation in vacuum and experiment for molecules in solution, highlighting the effectiveness of TDDFT for predicting optical properties of organic π-conjugated molecules. We then perform a statistical analysis based on molecular descriptors to identify which features are important in defining the absorption strength. This allows us to identify structural features that are correlated with high absorption strength in NFAs and could be used to guide molecular design: highly absorbing NFAs should possess a planar, linear, and fully conjugated molecular backbone with highly polarisable heteroatoms. We then exploit a random decision forest algorithm to draw predictions for ε d,max using a computational framework based on extended tight-binding Hamiltonians, which shows reasonable predicting accuracy with lower computational cost than TDDFT. This work provides a general understanding of the relationship between molecular structure and absorption strength in π-conjugated organic molecules, including NFAs, while introducing predictive machine-learning models of low computational cost., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The desired attributes of organic photovoltaics (OPV) as a low cost and sustainable energy harvesting technology demand the use of non-halogenated solvent processing for the photoactive layer (PAL) materials, preferably of low synthetic complexity (SC) and without compromising the power conversion efficiency (PCE). Despite their record PCEs, most donor-acceptor conjugated copolymers in combination with non-fullerene acceptors are still far from upscaling due to their high cost and SC. Here we present a non-halogenated and low SC ink formulation for the PAL of organic solar cells, comprising PTQ10 and PC 61 BM as donor and acceptor materials, respectively, showing a record PCE of 7.5% in blade coated devices under 1 sun, and 19.9% under indoor LED conditions. We further study the compatibility of the PAL with 5 different electron transport layers (ETLs) in inverted architecture. We identify that commercial ZnO-based formulations together with a methanol-based polyethyleneimine-Zn (PEI-Zn) chelated ETL ink are the most suitable interlayers for outdoor conditions, providing fill factors as high as 74% and excellent thickness tolerance (up to 150 nm for the ETL, and >200 nm for the PAL). In indoor environments, SnO 2 shows superior performance as it does not require UV photoactivation. Semi-transparent devices manufactured entirely in air via lamination show indoor PCEs exceeding 10% while retaining more than 80% of the initial performance after 400 and 350 hours of thermal and light stress, respectively. As a result, PTQ10:PC 61 BM combined with either PEI-Zn or SnO 2 is currently positioned as a promising system for industrialisation of low cost, multipurpose OPV modules., Competing Interests: O. I. and T. O. are co-founders of the company Epishine AB focused on commercializing OPV for indoor applications., (This journal is © The Royal Society of Chemistry.)

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-Ga 2 O 3 and a Kapton substrate (anisotropic), and (iii) a 285 nm thick SiO 2 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.

Electronic doping in organic materials has remained an elusive concept for several decades. It drew considerable attention in the early days in the quest for organic materials with high electrical conductivity, paving the way for the pioneering work on pristine organic semiconductors (OSCs) and their eventual use in a plethora of applications. Despite this early trend, however, recent strides in the field of organic electronics have been made hand in hand with the development and use of dopants to the point that are now ubiquitous. Here, we give an overview of all important advances in the area of doping of organic semiconductors and their applications. We first review the relevant literature with particular focus on the physical processes involved, discussing established mechanisms but also newly proposed theories. We then continue with a comprehensive summary of the most widely studied dopants to date, placing particular emphasis on the chemical strategies toward the synthesis of molecules with improved functionality. The processing routes toward doped organic films and the important doping-processing-nanostructure relationships, are also discussed. We conclude the review by highlighting how doping can enhance the operating characteristics of various organic devices.

Optimization of a new system for organic solar cells is a multiparametric analysis problem that requires substantial efforts in terms of time and resources. The strong microstructure-dependent performance of polymer:polymer cells makes them particularly difficult to optimize, or to translate previous knowledge from spin coating into more scalable techniques. In this work, the photovoltaic performance of blade-coated devices was studied based on the promising polymer:polymer system PBDB-T and PF5-Y5 as donor and acceptor, respectively. Using the recently developed high-throughput methodology, the system was optimized for multiple variables, including solvent system, active layer composition, ratio, and thickness, among others, by fabricating more than 500 devices with less than 24 mg of each component. As a result, the power conversion efficiency of the blade-coated devices varied from 0.08 to 6.43 % in the best device. The performed statistical analysis of the large experimental data obtained showed that solvent selection had the major impact on the final device performance due to its influence on the active layer microstructure. As a conclusion, the use of the plot of the device efficiency in the Hansen space was proposed as a powerful tool to guide solvent selection in organic photovoltaics., (© 2021 The Authors. ChemSusChem published by Wiley-VCH GmbH.)