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Many molecular semiconductors show a pronounced polymorphism; i.e. they can adopt different crystal arrangements depending, e.g., on temperature, pressure, and selected solidification pathways. This renders reliable fabrication of molecular semiconductor devices challenging, as minute changes in processing can lead to numerous structures and, hence, optoelectronic responses. Here, we demonstrate using the example of p-DTS(FBTTh2)2 that spatial confinement at the nanoscale can be exploited to detect specific polymorphs and the conditions under they form. A new polymorph exhibiting a higher charge-carrier mobility compared to previously reported p-DTS(FBTTh2)2 crystal forms is found at elevated temperatures and high degree of confinement, illustrating the benefit of our approach and promising that spatial confinement will find wide-spread application to understand and control polymorph formation in organic semiconductors.

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]: 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.

We demonstrate that the observed (in-)stability of n-doped carbon nanotube films in air not only depends on the employed dopant but is also strongly affected by sample-specific factors, such as the film thickness and density. We show this for two typical dopants, polyethylenimine and a potassium crown ether complex, by preparing films of increasing thickness. We argue that reports on dopant stability cannot be properly assessed without knowledge of these sample-specific parameters, which explains some of the conflicting results in the literature.

Organic photovoltaics (OPVs) are an emerging light-to-electricity conversion technology that promises flexible, lightweight, semitransparent devices based on abundant and non-toxic organic semiconductors. OPV power conversion efficiency under one sun has been increasing at an average pace of approximately 1% every year over the past 10 years, up to current values circa 20%. This has been possible through the continuous synthesis of improved semiconductors, particularly non-fullerene acceptors (NFAs), as well as a fine control of the microstructure.

Functionally graded materials (FGMs) are widely explored in the context of inorganic thermoelectrics, but not yet in organic thermoelectrics. Here, the impact of doping gradients on the thermoelectric properties of a chemically doped conjugated polymer is studied. The in-plane drift of counterions in moderate electric fields is used to create lateral doping gradients in films composed of a polythiophene with oligoether side chains, doped with 2,3,5,6-tetrafluoro-tetracyanoquinodimethane (F4TCNQ). Raman microscopy reveals that a bias voltage of as little as 5 V across a 50 µm wide channel is sufficient to trigger counterion drift, resulting in doping gradients. The effective electrical conductivity of the graded channel decreases with bias voltage, while an overall increase in Seebeck coefficient is observed, yielding an up to eight-fold enhancement in power factor. Kinetic Monte Carlo simulations of graded films explain the increase in power factor in terms of a roll-off of the Seebeck coefficient at high electrical conductivities in combination with a mobility decay due to increased Coulomb scattering at high dopant concentrations. Therefore, the FGM concept is found to be a way to improve the thermoelectric performance of not yet optimally doped organic semiconductors, which may ease the screening of new materials as well as the fabrication of devices.

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.

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.

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.

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 hi

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 new

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 mu W 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 mu W 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., Funding Agencies|European Union [955837]; Knut and Alice Wallenberg Foundation through a Wallenberg Academy Fellowship Prolongation grant; Spanish Ministerio de Ciencia e Innovacion [CEX2019-000917-S, PID2020-119777GBI00, PDC2021-121814-I00]; China Scholarship Council [CSC201806950006]; Universitat Autonoma de Barcelona

Organic solar cells are attracting attention due to being light-weight, low-cost and having tunable optical properties, which make them interesting for different applications such as integrated building and agrovoltaics. For such applications, the angle of incidence of light is given by architectural limitations and thus it is important to understand what controls the dependence of solar cell performance on the angle of incidence of light. Here the angular dependence for an organic solar cell is measured to quantify the effects of a reduction in light intensity, of an increased optical path within the active layer and of the angular variation of the reflection losses, Las células solares orgánicas llaman la atención por ser ligeras, de bajo coste y tener propiedades ópticas ajustables, lo que las hacen interesantes para diferentes aplicaciones como la construcción integrada y la agrovoltaica. Para estas aplicaciones, el ángulo de incidencia de la luz viene dado por limitaciones estructurales y, por tanto, es importante entender qué controla la dependencia del rendimiento de las células solares según el ángulo de incidencia de la luz. Aquí se mide la dependencia angular de una célula solar orgánica para cuantificar los efectos de la reducción de la intensidad de la luz, del aumento del camino óptico dentro de la capa activa y de la variación angular de las pérdidas de reflexión ., Les cèl·lules solars orgàniques capten l'atenció pel fet de ser lleugeres, de baix cost i de tenir propietats òptiques ajustables, cosa que les fan interessants per a diferents aplicacions com la construcció integrada i l'agrovoltaica. Per a aquestes aplicacions, l'angle d'incidència de la llum ve donat per limitacions estructurals i, per tant, és important entendre què controla la dependència del rendiment de les cèl·lules solars segons l'angle d'incidència de la llum. Aquí es mesura la dependència angular d'una cèl·lula solar orgànica per quantificar els efectes de la reducció de la intensitat de la llum, de l'augment del camí òptic dins de la capa activa i de la variació angular de les pèrdues de reflexió.

The integration of organic photovoltaic (OPV) modules on greenhouses is an encouraging practice to offset the energy demands of crop growth and provide extra functionality to dedicated farmland. Nevertheless, such OPV devices must meet certain optical and stability requirements to turn net zero energy greenhouse systems a reality. Here a donor:acceptor polymer blend is optimized for its use in laminated devices while matching the optical needs of crops. Optical modeling is performed and a greenhouse figure-of-merit is introduced to benchmark the trade-off between photovoltaic performance and transparency for both chloroplasts and humans. Balanced donor:acceptor ratios result in better-performing and more thermally stable devices than acceptor-enriched counterparts. The optimized polymer blend and state-of-the-art polymer:small-molecule blends are next transferred to 25 cm(2) laminated modules processed entirely from solution and in ambient conditions. The modules are mounted on a greenhouse as standalone or 4-terminal tandem configurations and their outdoor stability is tracked for months. The study reveals degradation modes undetectable under laboratory conditions such as module delamination, which accounts for 10-20% loss in active area. Among the active layers tested, polymer:fullerene blends are the most stable and position as robust light harvesters in future building-integrated OPV systems., Funding Agencies|Knut and Alice Wallenberg Foundation; Marie Sklodowska-Curie Actions [101025608]; Spanish Ministry of Science and Innovation [PID2021-128924OB-I00]

We present an innovative contactless method suitable to study in-plane thermal transport based on beam-offset frequency-domain thermoreflectance using a one-dimensional heat source with uniform power distribution. Using a one-dimensional heat source provides a number of advantages as compared to point-like heat sources, as typically used in time- and frequency-domain thermoreflectance experiments, just to name a few: (i) it leads to a slower spatial decay of the temperature field in the direction perpendicular to the line-shaped heat source, allowing to probe the temperature field at larger distances from the heater, hence, enhancing the sensitivity to in-plane thermal transport; (ii) the frequency range of interest is typically kHz. This rather low frequency range is convenient regarding the cost of the required excitation laser system but, most importantly, it allows the study of materials without the presence of a metallic transducer with almost no influence of the finite optical penetration depth of the pump and probe beams on the thermal phase lag, which arises from the large thermal penetration depth imposed by the used frequency range. We also show that for the case of a harmonic thermal excitation source, the phase lag between the thermal excitation and thermal response of the sample exhibits a linear dependence with their spatial offset, where the slope is proportional to the inverse of the thermal diffusivity of the material. We demonstrate the applicability of this method to the cases of: (i) suspended thin films of Si and PDPP4T, (ii) Bi bulk samples, and (iii) Si, glass, and highly-oriented pyrollitic graphite (HOPG) bulk samples with a thin metallic transducer. Finally, we also show that it is possible to study in-plane heat transport on substrates with rather low thermal diffusivity, e.g., glass, even using a metallic transducer. We achieve this by an original approach based on patterning the transducer using focused ion beam, with the key purpose of

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.

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 band gaps 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, namely PBDB-T-2F:IO-4Cl, PBDB-T-2F:Y6 and PTB7-Th:COTIC-4F, 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. This article is protected by copyright. All rights reserved.

[EN] Disclosed are a device and method for obtaining a tensor of thermal conductivity in isotropic and anisotropic materials, comprising: a first pump laser and a second probe laser with a shorter wavelength; a transducer, and a set of beam splitters arranged so as to bundle the laser beams along a common optical axis; a diffractive optical element (DOE), designed to convert, by means of diffraction, a beam with Gaussian distribution into a linear beam with uniform intensity distribution along the longitudinal axis and Gaussian distribution along the transverse axis; a balanced sensor, designed to receive the reflection from the beams and a sample from the probe laser beam, calculating the difference between the two; and a lock-in type amplifier, which receives a frequency-modulated signal that reflects the thermal oscillations of the sample surface and is used to obtain the thermal conductivity tensor., [ES] Equipo y método para la obtención de un tensor de conductividad térmica en materiales isótropos y anisótropos que comprende un primer láser de bombeo, un segundo láser sonda, con una longitud de onda menor; un transductor, un conjunto de divisores de haz dispuestos para unir los haces de los láseres en un eje óptico común; un elemento de difracción óptica (DOE), configurado para convertir mediante difracción un haz con distribución Gaussiana en un haz con forma de línea con distribución de intensidad uniforme en el eje longitudinal y distribución Gaussiana en el eje transversal; un detector balanceado, configurado para recibir la reflexión de los haces y una muestra del haz de laser sonda, calculando la diferencia entre ambos, un amplificador tipo "lock-in", que recibe una señal modulada en frecuencia que refleja las oscilaciones térmicas de la superficie de la muestra y se usa para obtener el tensor de conductividad térmica., [FR] La présente invention concerne un matériel et une méthode pour l'obtention d'un tenseur de conductivité thermique dans des matériaux isotropes et anisotropes qui comprend un premier laser de pompage, un second laser sonde, ayant une longueur d'onde inférieure; un transducteur, un ensemble de diviseurs de faisceau disposés pour combiner les faisceaux des lasers sur un axe optique commun; un élément de diffraction optique (DOE), configuré pour convertir par diffraction un faisceau ayant une distribution Gaussienne en un faisceau de forme linéaire ayant une distribution d'intensité uniforme sur l'axe longitudinal et une distribution Gaussienne sur l'axe transversal; un détecteur équilibré, configuré pour recevoir la réflexion des faisceaux et un échantillon du faisceau de laser sonde, un amplificateur de type "lock-in" calculant la différence entre les deux, lequel amplificateur reçoit un signal modulé en fréquence qui reflète les oscillations thermiques de la surface de l'échantillon et qui est utilisé pour obtenir le tenseur de conductivité thermique.

[ES] Equipo y método para la obtención de un tensor de conductividad térmica en materiales isótropos y anisótropos que comprende un primer láser de bombeo, un segundo láser sonda, con una longitud de onda menor; un transductor, un conjunto de divisores de haz dispuestos para unir los haces de los láseres en un eje óptico común; un elemento de difracción óptica (DOE), configurado para convertir mediante difracción un haz con distribución Gaussiana en un haz con forma de línea con distribución de intensidad uniforme en el eje longitudinal y distribución Gaussiana en el eje transversal; un detector balanceado, configurado para recibir la reflexión de los haces y una muestra del haz de laser sonda, calculando la diferencia entre ambos, un amplificador tipo "lock-in", que recibe una señal modulada en frecuencia que refleja las oscilaciones térmicas de la superficie de la muestra y se usa para obtener el tensor de conductividad térmica., [EN] Disclosed are a device and method for obtaining a tensor of thermal conductivity in isotropic and anisotropic materials, comprising: a first pump laser and a second probe laser with a shorter wavelength; a transducer, and a set of beam splitters arranged so as to bundle the laser beams along a common optical axis; a diffractive optical element (DOE), designed to convert, by means of diffraction, a beam with Gaussian distribution into a linear beam with uniform intensity distribution along the longitudinal axis and Gaussian distribution along the transverse axis; a balanced sensor, designed to receive the reflection from the beams and a sample from the probe laser beam, calculating the difference between the two; and a lock-in type amplifier, which receives a frequency-modulated signal that reflects the thermal oscillations of the sample surface and is used to obtain the thermal conductivity tensor.

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., Funding Agencies|Spanish Ministry of Science and Innovation through the Severo Ochoa"Program for Centers of Excellence in RD [CEX2019-000917-S, PGC2018-095411-B I00]; European Research Council (ERC)European Research Council (ERC)European Commission [648901]

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 PC61BM 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, SnO2 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:PC61BM combined with either PEI-Zn or SnO2 is currently positioned as a promising system for industrialisation of low cost, multipurpose OPV modules., Funding Agencies|Knut and Alice Wallenberg foundationKnut & Alice Wallenberg Foundation; Ministry of Science and InnovationSpanish Government [CEX2019-000917-S, PGC2018-095411-B-I00]; European Research CouncilEuropean Research Council (ERC)European Commission [648901]

While it is widely recognized that microstructure plays an important role in the performance of organic photovoltaics (OPV), systematic studies are often challenging, as varying the molecular packing through typical chemical means (such as sidechain tuning) often affects the molecular energy levels, thus preventing a clear correlation. In this work we present the synthesis of three perylene imide (PI) based electron acceptors with almost identical energy levels, but distinct packing tendencies. We confirm our initial hypothesis by measuring solution and solid-state absorption, and cyclic voltammetry as well as characterizing the films by grazing incidence wide angle X-ray scattering (GIWAXS). In a second step, we repeat the characterization of the three materials in blends with two polymer donors, namely PCDTBT or PBDBT, whose energy levels are well aligned with those of the PI acceptors, and which, additionally, exhibit different degrees of structural order. We show how the initial strong difference between acceptors is partially blurred in blends, but still critical. Finally, we correlate our structural data with OPV devices made with the corresponding six blends. Our data suggest that a good donor acceptor marriage should ensure good energy alignment but also exhibit complementary crystallization tendencies of the two components.

A combinatorial study of the effect of in-mixing of various guests on the thermoelectric properties of the host workhorse polymer poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) is presented. Specifically, the composition and thickness for doped films of PBTTT blended with different polymers are varied. Some blends at guest weight fractions around 10-15% exhibit up to a fivefold increase in power factor compared to the reference material, leading to zT values around 0.1. Spectroscopic analysis of the charge-transfer species, structural characterization using grazing-incidence wide-angle X-ray scattering, differential scanning calorimetry, Raman, and atomic force microscopy, and Monte Carlo simulations are employed to determine that the key to improved performance is for the guest to promote long-range electrical connectivity and low disorder, together with similar highest occupied molecular orbital levels for both materials in order to ensure electronic connectivity are combined., Funding Agencies|Spanish Ministry of Science and InnovationSpanish Government [CEX2019-000917-S, PGC2018-095411- B-I00, PGC2018-094620-A-I00, MAT2017-90024-P]; European Research Council (ERC)European Research Council (ERC)European Commission [648901, 963954]; Ministerio de Ciencia, Innovacion y UniversidadesSpanish Government; European Regional Development FundEuropean Commission; European Social FundEuropean Social Fund (ESF); CSIC Open Access Publication Support Initiative through its Unidad de Recursos de Informacion Cientifica para la Investigacion (URICI); Carl Zeiss Foundation; Alexander von Humboldt FoundationAlexander von Humboldt Foundation

The integration of organic photovoltaic (OPV) modules on greenhouses is an encouraging practice to offset the energy demands of crop growth and provide extra functionality to dedicated farmland. Nevertheless, such OPV devices must meet certain optical and stability requirements to turn net zero energy greenhouse systems a reality. Here a donor:acceptor polymer blend is optimized for its use in laminated devices while matching the optical needs of crops. Optical modeling is performed and a greenhouse figure-of-merit is introduced to benchmark the trade-off between photovoltaic performance and transparency for both chloroplasts and humans. Balanced donor:acceptor ratios result in better-performing and more thermally stable devices than acceptor-enriched counterparts. The optimized polymer blend and state-of-the-art polymer:small-molecule blends are next transferred to 25 cm2 laminated modules processed entirely from solution and in ambient conditions. The modules are mounted on a greenhouse as standalone or 4-terminal tandem configurations and their outdoor stability is tracked for months. The study reveals degradation modes undetectable under laboratory conditions such as module delamination, which accounts for 10–20% loss in active area. Among the active layers tested, polymer:fullerene blends are the most stable and position as robust light harvesters in future building-integrated OPV systems.

[Abastract]: 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 liquidcrystalline 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 investigati

The fabrication of efficient organic photovoltaic (OPV) modules via high throughput methods is a crucial milestone to facilitate their commercialization. The achievement of reliable printing and coating processes for large-scale modules has, however, been challenging thus far. Indeed, the performance gap is large between cells produced at lab-scale and those resulting from industrial methods. Therefore, understanding the critical steps in the upscaling process is decisive to address the research efforts towards decreasing the aforementioned gap. In this contribution, we analyze the efficiency losses associated with several of the main steps involved in the up-scaling pathway of the OPV devices, from lab-scale blade coating to pre-industrial slot die roll-to-roll coating. We show that when using materials in the active layer for which the performance is tolerant to thickness/microstructure variations, the critical steps are related to the charge carrier blocking layers, as well as potential losses due to parasitic absorption in the semitransparent electrodes.

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 PC61BM 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, SnO2 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:PC61BM combined with either PEI-Zn or SnO2 is currently positioned as a promising system for industrialisation of low cost, multipurpose OPV modules.

A combinatorial study of the effect of in-mixing of various guests on the thermoelectric properties of the host workhorse polymer poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) is presented. Specifically, the composition and thickness for doped films of PBTTT blended with different polymers are varied. Some blends at guest weight fractions around 10–15% exhibit up to a fivefold increase in power factor compared to the reference material, leading to zT values around 0.1. Spectroscopic analysis of the charge-transfer species, structural characterization using grazing-incidence wide-angle X-ray scattering, differential scanning calorimetry, Raman, and atomic force microscopy, and Monte Carlo simulations are employed to determine that the key to improved performance is for the guest to promote long-range electrical connectivity and low disorder, together with similar highest occupied molecular orbital levels for both materials in order to ensure electronic connectivity are combined.

[Abstract] While it is widely recognized that microstructure plays an important role in the performance of organic photovoltaics (OPV), systematic studies are often challenging, as varying the molecular packing through typical chemical means (such as sidechain tuning) often affects the molecular energy levels, thus preventing a clear correlation. In this work we present the synthesis of three perylene imide (PI) based electron acceptors with almost identical energy levels, but distinct packing tendencies. We confirm our initial hypothesis by measuring solution and solid-state absorption, and cyclic voltammetry as well as characterizing the films by grazing incidence wide angle X-ray scattering (GIWAXS). In a second step, we repeat the characterization of the three materials in blends with two polymer donors, namely PCDTBT or PBDBT, whose energy levels are well aligned with those of the PI acceptors, and which, additionally, exhibit different degrees of structural order. We show how the initial strong difference between acceptors is partially blurred in blends, but still critical. Finally, we correlate our structural data with OPV devices made with the corresponding six blends. Our data suggest that a good donor acceptor marriage should ensure good energy alignment but also exhibit complementary crystallization tendencies of the two components.

While it is widely recognized that microstructure plays an important role in the performance of organic photovoltaics (OPV), systematic studies are often challenging, as varying the molecular packing through typical chemical means (such as sidechain tuning) often affects the molecular energy levels, thus preventing a clear correlation. In this work we present the synthesis of three perylene imide (PI) based electron acceptors with almost identical energy levels, but distinct packing tendencies. We confirm our initial hypothesis by measuring solution and solid-state absorption, cyclic voltammetry as well as characterizing the films by grazing incident wide angle X-ray scattering (GIWAXS). In a second step, we repeat the characterization of the three materials in blends with two polymer donors, namely PCDTBT or PBDBT, whose energy levels are well aligned with those of the PI acceptors, and which, additionally, exhibit different degrees of structural order. We show how the initial strong difference between acceptors is partially blurred in blends, but still critical. Finally, we correlate our structural data with OPV devices made with the corresponding six blends. Our data suggest that a good donor acceptor marriage should ensure good energy alignment but also exhibit complementary crystallization tendencies of the two components.

The dataset here provided corresponds to the open access article with DOI 10.1002/aenm.201902417. The package contains the raw data (Raman spectra, photocurrent, photoluminescence, reflectivity) extracted from ternary organic solar cells processed following combinatorial schemes. The datasets used to build the figures of the main article are included as well to reproduce the depicted illustrations.

Combining non-fullerene acceptors (NFAs) with novel low band gap polymers has led to very promising performances. However, research on donors that can reduce the performance–cost gap, such as poly(3-hexylthiophene) (P3HT), can play an instrumental role in the upscaling of this technology. In this paper, we have analysed the influence of several processing parameters on the performance of solar cells based on P3HT:NFA binaries deposited by blade coating. The investigated NFAs include molecules with variations in the side chains and end-capping groups. More precisely, we have looked at devices based on P3HT blended with five NFAs, namely ITIC, ITIC-M, O-IDTBR, EH-IDTBR, and O-IDFBR, and employed PC60BM and ICBA as reference acceptors. More than one thousand doctor-bladed P3HT:NFA samples were manufactured using high throughput techniques using gradients of both thickness and annealing temperature. The combined data for all samples were employed to perform a parameter sensitivity study in order to identify the most influential parameters for P3HT based devices. For all material combinations, we have found that blade coated solar cells fabricated from chlorobenzene/dichlorobenzene mixtures outperform those based on chlorobenzene. For the most promising binary (i.e. P3HT:O-IDTBR), we have investigated in more depth the effects resulting from the choice of solvent, as well as casting temperature and post-deposition thermal annealing. Devices with power conversion efficiencies greater than 5% were obtained regardless of the casting temperature and for a relatively wide thickness range (80–250 nm). Finally, we have shown that encapsulated devices exhibit a stable performance for more than 3000 h and that degradation progresses faster in thicker devices. O-IDTBR has been identified to play a major role in the device degradation.

Direct piezoelectric force microscopy (DPFM) is employed to examine whether or not lead halide perovskites exhibit ferroelectricity. Compared to conventional piezoelectric force microscopy, DPFM is a novel technique capable of measuring piezoelectricity directly. This fact is fundamental to be able to examine the existence of ferroelectricity in lead halide perovskites, an issue that has been under debate for several years. DPFM is used to detect the current signals, i.e. changes in the charge distribution under the influence of the scan direction and applied force of the atomic force microscope (AFM) tip in contact mode. For comparison, (i) we use DPFM on lead halide perovskites and well-known ferroelectric materials (i.e. periodically poled lithium niobate and lead zirconate titanate); and (ii) we conduct parallel experiments on MAPbI3 films of different grain sizes, film thicknesses, substrates, and textures using DPFM as well as piezoelectric force microscopy (PFM) and electrostatic force microscopy (EFM). In contrast to previous work that claimed there were ferroelectric domains in MAPbI3 perovskite films, our work shows that the studied perovskite films Cs0.05(FA0.83MA0.17)0.95Pb(I0.83Br0.17)3 and MAPbI3 are ferroelectricity-free. The observed current profiles of lead halide perovskites possibly originate from ion migration that happens under an applied electrical bias and in strained samples under mechanical stress. This work provides a deeper understanding of the fundamental physical properties of the organic–inorganic lead halide perovskites and solves a longstanding dispute about their non-ferroelectric character: an issue of high relevance for optoelectronic and photovoltaic applications.

The generally low energy density from most heat sources—the Sun, Earth as well as most human activities—implies that solid-state thermoelectric devices are the most versatile heat harvesters since, unlike steam engines, they can be used on a small scale and at small temperature differences. In this opinion piece, we first discuss the materials requirements for the widespread use of thermoelectrics. We argue that carbon-based materials, such as conducting polymers and carbon nanotubes, are particularly suited for large area and low-temperature operation applications, as they are abundant, low-toxicity and easy to process. We combine experimentally observed macro-trends and basic thermoelectric relations to evaluate the major performance limitations of this technology thus far and propose a number of avenues to take the thermoelectric efficiency of organic materials beyond the state of the art. First, we emphasize how charge carrier mobility, rather than charge density, is currently limiting performance, and discuss how to improve mobility by exploiting anisotropy, high persistence length materials and composites with long and well-dispersed carbon nanotubes. We also show that reducing thermal conductivity could double efficiency while reducing doping requirements. Finally, we discuss several ways in which composites could further boost performance, introducing the concept of interface engineering to produce phonon stack-electron tunnel composites.This article is part of a discussion meeting issue ‘Energy materials for a low carbon future'.

En l'actual era de la Internet de les Coses (de l'anglès, IOT), els dispositius de detecció intel·ligents estan canviant molt el món en què vivim, des de com percebem el nostre entorn fins a com gastem l'energia. Fonts d'energia per a aquests dispositius seran essencials, especialment si no requereixen manteniment, són flexibles, barates, altament processable o fins i tot d'un sol ús. Els materials termoelèctrics orgànics --- semiconductors que poden transformar la calor en electricitat --- poden complir aquestes característiques. No obstant això, en els materials d'última generació encara hi ha aspectes que necessiten ser millorats; com el rendiment termoelèctric, estimat mitjançant la figura de mèrit ZT i l'estabilitat termoelèctrica sota continu estrès tèrmic. Aquesta tesi informa sobre estratègies per millorar l'eficiència i estabilitat termoelèctriques. Com a sistema de referència fem servir PBTTT dopat amb l'acceptor molecular F4TCNQ. Com a eina transversal per als nostres estudis, desenvolupem mètodes de fabricació i caracterització d'alt rendiment basats en gradients de tractament tèrmic, dopat i gruix per estudiar i correlacionar la relació entre la microestructura, les propietats termoelèctriques i l'estabilitat en una gran quantitat de mostres. A la primera secció de resultats proposem una estratègia per millorar l'estabilitat termoelèctrica. Hem demostrat que la formació de complexos de càrrega (CTC per les seves sigles en anglès) generen mostres tèrmicament més resistents, encara que elèctricament menys conductores. Al desenvolupar un mètode per ajustar la relació de transferència de càrrega parcial a una transferència completa, podem millorar l'estabilitat a llarg termini sense sacrificar la conductivitat elèctrica. La segona secció de resultats aborda la relació entre la cristal·linitat, el transport tèrmic i el transport elèctric. Hem demostrat que el grau de cristal·linitat determina en gran mesura la conductivitat tèrmica de capa fina de polímer. U, En la actual era de la Internet de las Cosas (del inglés, IoT), los dispositivos de detección inteligentes están cambiando mucho del mundo en el que vivimos, desde cómo percibimos nuestro entorno hasta cómo gastamos la energía. Fuentes de energía para tales dispositivos serán esenciales, especialmente si no requieren mantenimiento, son flexibles, baratas, altamente procesable o incluso desechables. Los materiales termoeléctricos orgánicos --- semiconductores que pueden transformar el calor en electricidad --- pueden cumplir estas características. Sin embargo, en los materiales de última generación todavía hay aspectos que necesitan ser mejorados; como el rendimiento termoeléctrico, estimado mediante la figura de mérito ZT y la estabilidad termoeléctrica bajo continuo estrés térmico. Esta tesis informa sobre estrategias para mejorar la eficiencia y estabilidad termoeléctricas. Como sistema de referencia empleamos PBTTT dopado con el aceptor molecular F4TCNQ. Como herramienta transversal para nuestros estudios, desarrollamos métodos de fabricación y caracterización de alto rendimiento basados en gradientes de tratamiento térmico, dopado y espesor para estudiar y correlacionar la relación entre la microestructura, las propiedades termoeléctricas y la estabilidad en una gran cantidad de muestras. En la primera sección de resultados proponemos una estrategia para mejorar la estabilidad termoeléctrica. Demostramos que la formación de complejos de carga (CTC) generan muestras térmicamente más resistentes, aunque menos eléctricamente menos conductora. Al desarrollar un método para ajustar la relación de transferencia de carga parcial a entera, podemos mejorar la estabilidad a largo plazo sin sacrificar la conductividad eléctrica. La segunda sección de resultados aborda la relación entre cristalinidad, transporte térmico y eléctrico. Demostramos que el grado de cristalinidad determina en gran medida la conductividad térmica de capa fina de polímero. Tras dopar, incluso un co, In the current Internet of Things (IoT) era, smart sensing-devices are changing much about the world we live in, from how we sense our surroundings to the way we spend energy. On-site power generators for such devices will be essential, especially if they are maintenance-free, flexible, cheap, printable, or even disposable. Organic thermoelectric materials --- semiconductors that can transform heat into electricity at near-room temperature --- can fulfill these characteristics. Nevertheless, there are still issues in the current state-of-the-art materials that need improvement, such as the thermoelectric performance, benchmarked by the dimensionless ZT, and the thermoelectric stability under continuous thermal stress. This thesis reports on strategies to improve thermoelectric efficiency and stability. As a testbed material system, we employ PBTTT doped with the molecular acceptor F4TCNQ. As a transversal tool for our studies, we developed high-throughput fabrication and characterization methods based on annealing-, doping- and thickness-gradients to study and correlate the relationship between microstructure, thermoelectric properties, and stability for many samples. The first set of results reports on a strategy to improve thermoelectric stability. We demonstrate that the formation of charge transfer complexes (CTCs) leads to more thermally enduring samples, although less electrically conductive. By developing a method to adjust the partial to integer charge-transfer ratio, we can improve the long-term stability without sacrificing the electrical conductivity. The subsequent chapter centers on the relationship between crystallinity and thermal and electric transport. We demonstrate that the degree of crystallinity largely determines the thermal conductivity of the film. Upon doping, even a relatively small dopant content increases the electrical conductivity several orders of magnitude but lowers the thermal conductivity without noticeable deterioration in the cry, Universitat Autònoma de Barcelona. Programa de Doctorat en Ciència de Materials

Organic solar cells incorporating non-fullerene acceptors (NFAs) have reached remarkable power conversion efficiencies of over 18%. Unlike fullerene derivatives, NFAs tend to crystallize from solutions, resulting in bulk heterojunctions that include a crystalline acceptor phase. This must be considered in any morphology-function models. Here, it is confirmed that high-performing solution-processed indacenodithienothiophene-based NFAs, i.e., ITIC and its derivatives ITIC-M, ITIC-2F, and ITIC-Th, exhibit at least two crystalline forms. In addition to highly ordered polymorphs that form at high temperatures, NFAs arrange into a low-temperature metastable phase that is readily promoted via solution processing and leads to the highest device efficiencies. Intriguingly, the low-temperature forms seem to feature a continuous network that favors charge transport despite of a poorly order along the pi-pi stacking direction. As the optical absorption of the structurally more disordered low-temperature phase can surpass that of the more ordered polymorphs while displaying comparable-or even higher-charge transport properties, it is argued that such a packing structure is an important feature for reaching highest device efficiencies, thus, providing guidelines for future materials design and crystal engineering activities.

Actualment, un dels reptes en l'àmbit de la manipulació de la llum a la nanoescala és la transició del laboratori a aplicacions reals. Tot i el gran potencial demostrat per algunes estructures fotòniques per a incrementar la eficiència de instruments optoelectrònics, la seva implementació de d'aquestes a dispositius de mercat sovint es obstruïda per la necessitat d'usar tècniques de fabricació poc escalables i d'alt cost. Aquesta tesis està dedicada al disseny i implementació de estratègies de manipulació de la llum per a millorar la eficiència en la recol·lecció d'energia de plaques solars i fotodetectors, així com la millora de la emissió en dispositius d'il·luminació, mitjançant mètodes de nanoestructuració escalables com la nano-litografia suau. Aquesta tècnica té la capacitat de produir patrons i estructures amb una resolució de pocs nanòmetres amb gran fidelitat en àrees grans. A més a més, és compatible amb el processament a gran escala mitjançant el sistema de impressió en cadena "roll to roll" (carret-a-carret). També es tracta d'una tecnologia molt versàtil, ja que permet l'ús de diferents tipus de substrats, és poc invasiva i generalment pot ser introduïda en el esquema de fabricació sense haver de modificar cap pas. Amb l'ajuda d'aquesta tècnica de nanofabricació, explorem una varietat de arquitectures fotòniques i les diferents ressonàncies fotòniques que les fan especials. Entre aquestes darreres podem trobar ressonàncies de Mie, modes de Brewster i modes de cristall fotònic, que proveiran al sistema amb una major interacció llum-matèria a la capa activa del dispositiu, podent-ne millorar les seves capacitats òptiques. Primer, hem desenvolupat una estratègia per aconseguir una absorció optima de banda ample en semiconductors ultra-fins, amb menys de 100 nm de gruix, per a totes les energies per sobre de la seva energia de banda prohibida. La sinèrgia de les fortes ressonàncies d'interferència de capes fines presents i els modes del cristall fotònic de, Actualmente, uno de los retos en el ámbito de la manipulación de la luz a la nanoescala es la transición del laboratorio a aplicaciones reales. A pesar del gran potencial demostrado por algunas estructuras fotónicas para incrementar la eficiencia de instrumentos optoelectrónicos, su implementación en dispositivos de mercado muchas veces es obstruida por la necesidad de utilizar técnicas de fabricación poco escalables y de alto coste. Esta tesis está dedicada al diseño e implementación de estrategias de manipulación de la luz para mejorar la eficiencia en la recolección de energía de placas solares y fotodetectores, así como la mejora de la emisión en dispositivos de iluminación, mediante métodos de nanoestructuración escalables como la nano-litografía suave. Esta técnica tiene la capacidad de producir patrones y estructures con una resolución de pocos nanómetros con gran fidelidad en áreas grandes. Encima, es compatible con el procesamiento a gran escala mediante el sistema de impresión en cadena "roll-to-roll" (carrete-a-carrete). También se trata de una tecnología muy versátil, puesto que permite el uso de diferentes tipos de sustratos, es poco invasiva y generalmente puede ser introducida en el esquema de fabricación sin tener que modificar ningún paso. Con la ayuda de esta técnica de nanofabricación, exploramos una variedad de arquitecturas fotónicas y las diferentes resonancias fotónicas que las hacen especiales. Entre estas últimas podemos encontrar resonancias de Mie, modos de Brewster y modos de cristal fotónico, que proveerán al sistema con una mayor interacción luz-materia a la capa activa del dispositivo, mejorar sus capacidades ópticas. Primero, hemos desarrollado una estrategia para conseguir una absorción óptima de banda ancha en semiconductores ultra-finos, con menos de 100 nm de grosor, para todas las energías por encima de su energía de banda prohibida. La sinergia de las fuertes resonancias de interferencia de capas finas presentes y los modos del, Currently, one of the main challenges in light management at the nanoscale is the transition from the laboratory to real applications. Despite the great potential shown by photonic architectures to optically improve the performance of many devices, transitioning into marketable devices is often hampered by the low-throughput and expensive nanofabrication techniques involved. This thesis is devoted to the design and development of subwavelength light managing strategies to improve the light harvesting or out-coupling in solar cells, photodetectors and light emitters while using a scalable nanostructuration such as soft nanoimprint lithography (NIL). This technique has been proven to achieve resolutions down to few tens of nanometers with high fidelity in large areas, being compatible with roll to roll processing. It is also versatile regarding the materials where it can be used, non-invasive, and can be seamlessly introduced in the devices fabrication scheme. With the aid of this technique, we explore a variety of photonic architectures and the different types of resonances sustained, from Brewster modes to Mie resonances, in order to enhance the light-matter interaction with the active layer of the device. First, we develop a strategy to achieve broadband optimal absorption in ultra-thin semiconductor materials (less than 100 nm thick) for all energies above their bandgap. The interplay of strong interference thin film resonances and photonic crystal modes sustained by a high refractive index nanostructure on a gold film renders the system with a 81% total absorption over a broad spectral range (from 400 to 1500 nm). Second, we combine soft NIL and chemical vapor deposition to obtain an array of silicon hemispheres on top of a high refractive index dielectric waveguide. We study the Mie resonances supported by the substrate, how these hybridize with the guided modes of the waveguide and how their interaction influences the electromagnetic near field of the metasurfa, Universitat Autònoma de Barcelona. Programa de Doctorat en Ciència de Materials

The invention relates to a method for providing a structural and/or a compositional modification in a molecular semiconductor target film by means of a thermal, a solvent vapour or a light stimulus that locally activates diffusion of functional molecules of a solution-deposited donor layer into the molecular semiconductor target film through a transitory interlayer. Therefore, the present invention could be included in the field of manufacturing of electronic, optoelectronic and photonic devices and structures based on molecular semiconductor materials.