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Given the broad use of nanostructured crystalline titania films, an environmentally friendly and more sustainable synthesis route is highly desirable. Here, a water-based, low-temperature route is presented to synthesize nanostructured foam-like crystalline titania films. A pearl necklace-like nanostructure is introduced as tailored titania morphology via biotemplating with the use of the major bovine whey protein ß-lactoglobulin (ß-lg). It is shown that titania crystallization in a brookite-anatase mixed phase is promoted via spray deposition at a comparatively low temperature of 120 °C. The obtained crystallites have an average grain size of (4.2 ± 0.3) nm. In situ grazing incidence small-angle and wide-angle X-ray scattering (GISAXS/GIWAXS) are simultaneously performed to understand the kinetics of film formation and the templating role of ß-lg during spray coating. In the ß-lg:titania biohybrid composites, the crystal growth in semicrystalline titania clusters is sterically directed by the condensing ß-lg biomatrix. Due to using spray coating, the green chemistry approach to titania-based functional films can be scaled up on a large scale, which can potentially be used in photocatalytic processes or systems related to energy application., QC 20221107

Printed paper-based electronics offers solutions to rising energy concerns by supplying flexible, environmentally friendly, low-cost infrastructure for portable and wearable electronics. Herein, we demonstrate a scalable spray-coating approach to fabricate tailored paper poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/cellulose nanofibril (CNF) electrodes for all-printed supercapacitors. Layer-by-layer spray deposition was used to achieve high-quality electrodes with optimized electrode thickness. The morphology of these electrodes was analyzed using advanced X-ray scattering methods, revealing that spray-coated electrodes have smaller agglomerations, resulting in a homogeneous film, ultimately suggesting a better electrode manufacturing method than drop-casting. The printed paper-based supercapacitors exhibit an areal capacitance of 9.1 mF/cm(2), which provides enough energy to power electrochromic indicators. The measured equivalent series resistance (ESR) is as low as 0.3 Omega, due to improved contact and homogeneous electrodes. In addition, a demonstrator in the form of a self-powered wearable wristband is shown, where a large-area (90 cm(2)) supercapacitor is integrated with a flexible solar cell and charged by ambient indoor light. This demonstration shows the tremendous potential for sequential coating/printing methods in the scaling up of printed wearables and self-sustaining systems., Funding Agencies|Swedish Foundation for Strategic Research; Knut and Alice Wallenberg Foundation (Wallenberg Wood Science Center); Onnesjo Foundation; EU SYMPHONY project (H2020) [862095]; DESY Strategic Fund (DSF)

Titanium dioxide (TiO2) is an excellent candidate material for semiconductor metal oxide-based substrates for surface-enhanced Raman scattering (SERS). Biotemplated fabrication of TiO2 thin films with a 3D network is a promising route for effectively transferring the morphology and ordering of the template into the TiO2 layer. The control over the crystallinity of TiO2 remains a challenge due to the low thermal stability of biopolymers. Here is reported a novel strategy of the cellulose nanofibril (CNF)-directed assembly of TiO2/CNF thin films with tailored morphology and crystallinity as SERS substrates. Polymorphous TiO2/CNF thin films with well-defined morphology are obtained by combining atomic layer deposition and thermal annealing. A high enhancement factor of 1.79 × 106 in terms of semiconductor metal oxide nanomaterial (SMON)-based SERS substrates is obtained from the annealed TiO2/CNF thin films with a TiO2 layer thickness of 10 nm fabricated on indium tin oxide (ITO), when probed by 4-mercaptobenzoic acid molecules. Common SERS probes down to 10 nm can be detected on these TiO2/CNF substrates, indicating superior sensitivity of TiO2/CNF thin films among SMON SERS substrates. This improvement in SERS sensitivity is realized through a cooperative modulation of the template morphology of the CNF network and the crystalline state of TiO2., QC 20220524

The rapid growth of digital information in the world necessitates a big leap in improving the existing technologies for magnetic recording. For the best modern perpendicular recording, the highest coercivity materials with minimal volume are required. We present a study of a facile technology for establishing mono- and multilayer surfaces from various single-domain flat magnetic nanoparticles that exhibit a strong perpendicular-oriented magnetic moment on solid and flexible substrates. Surfactant-free, hard ferromagnetic, and single-domain anisotropic strontium hexaferrite SrFe12O19nanoparticles with a perpendicular magnetic moment orientation and two different aspect ratios are self-ordered into magnetic thin nanofilms, exploiting the templating effect of cellulose nanofibrils and magnetic fields. Uniform magnetic coatings obtained by the scalable layer-by-layer spray deposition from a monolayer coverage up to thicknesses of a few tens of nanometers show a preferred in-plane orientation of the hard-magnetic nanoparticles. High coercivities of the films of up to 5 kOe and a high perpendicular anisotropy of Mr⊥/Ms> 80% are found. The application of the magnetic field during film deposition ensures additional improvement in perpendicular magnetic anisotropy and the appearance of residual magnetization in the film of up to 0.6Ms. For low-aspect-ratio nanoparticles stacked in periodic planar structures, the signs of the photonic band gap are revealed. The ability to create scalable, thin magnetic structures based on nanosized particles/building blocks opens great opportunities for their application in a wide variety of optoelectronic and magnetic storage devices., QC 20230421

The search for sustainable material solutions has put lignin as one of the prime candidates for aromatic building blocks in macromolecular materials. The present study aimed to demonstrate how lignin-based thermoset resins can be utilized in combination with different cross-linkers. Kraft lignin was used to produce thermosets with tunable mechanical and morphological properties. The lignin-based thermosets were obtained via a thermally induced thiol–ene reaction. The first part of this work was focused on Kraft lignin solvent fractionation and chemical modification of the ethanol soluble fraction. Chemical analysis indicated that the allylation process was selective toward phenolic hydroxyl groups. SAXS and SEM studies demonstrated that solvent fractionation and allylation processes affected the molecular and nanoscale morphological characteristics of lignin. The second part’s focus was on how the properties of thermosets can be tuned by using three different cross-linkers. The dynamic mechanical and morphological properties of three different thermosets were investigated via DMA, SAXS, and WAXS techniques. The three different thermosets exhibit similar molecular morphology but different storage modulus and glass transition temperature. In this work, it was shown that despite lignin’s heterogeneity it was possible to produce thermosetting materials with tunable properties., QC 20210217

Based on a diblock-copolymer templated sol–gel synthesis, germanium nanocrystals (GeNCs) are introduced to tailor mesoporous titania (TiO2) films for obtaining more efficient anodes for photovoltaic applications. After thermal annealing in air, the hybrid films with different GeNC content are investigated and compared with films undergoing an argon atmosphere annealing. The surface and inner morphologies of the TiO2/GeOx nanocomposite films are probed via scanning electron microscopy and grazing-incidence small-angle X-ray scattering. The crystal phase, chemical composition, and optical properties of the nanocomposite films are examined with transmission electron microscopy, X-ray photoelectron spectroscopy, and ultraviolet–visible spectroscopy. Special focus is set on the air-annealed nanocomposite films since they hold greater promise for photovoltaics. Specifically, the charge–carrier dynamics of these air-annealed nanocomposite films are studied, and it is found that, compared with pristine TiO2 photoanodes, the GeNC addition enhances the electron transfer, yielding an increase in the short-circuit photocurrent density of exemplary perovskite solar cells and thus, an enhanced device efficiency as well as a significantly reduced hysteresis., QC 20220321

In times where research focuses on the use of organic polymers as a base for complex organic electronic applications and improving device efficiencies, degradation is still less intensively addressed in fundamental studies. Hence, advanced neutron scattering methods are applied to investigate a model system for organic electronics composed of the widely used conductive polymer blend poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) together with nanocellulose as flexible reinforcing template material. In particular, the impact of relative humidity (RH) on the nanostructure evolution is studied in detail. The implications are discussed from a device performance point of view and the changing nanostructure is correlated with macroscale physical properties such as conductivity. The first humidification (95% RH) leads to an irreversible decrease of conductivity. After the first humidification cycle, however, the conductivity can be reversibly regained when returning to low humidity values (5% RH), which is important for device manufacturing. This finding can directly contribute to an improved usability of emerging organic electronics in daily live., QC 20220228

Large-scale fabrication of metal cluster layers for usage in sensor applications and photovoltaics is a huge challenge. Physical vapor deposition offers large-scale fabrication of metal cluster layers on templates and polymer surfaces. In the case of aluminum (Al), only little is known about the formation and interaction of Al clusters during sputter deposition. Complex polymer surface morphologies can tailor the deposited Al cluster layer. Here, a poly(methyl methacrylate)-block-poly(3-hexylthiophen-2,5-diyl) (PMMA-b-P3HT) diblock copolymer template is used to investigate the nanostructure formation of Al cluster layers on the different polymer domains and to compare it with the respective homopolymers PMMA and P3HT. The optical properties relevant for sensor applications are monitored with ultraviolet-visible (UV-vis) measurements during the sputter deposition. The formation of Al clusters is followed in situ with grazing-incidence small-angle X-ray scattering (GISAXS), and the chemical interaction is revealed by X-ray photoelectron spectroscopy (XPS). Furthermore, atomic force microscopy (AFM) and field emission scanning electron microscopy (FESEM) yield topographical information about selective wetting of Al on the P3HT domains and embedding in the PMMA domains in the early stages, followed by four distinct growth stages describing the Al nanostructure formation., QC 20220221

Optically responsive materials are present in everyday life, from screens to sensors. However, fabricating large-area, fossil-free materials for functional biocompatible applications is still a challenge today. Nanocelluloses from various sources, such as wood, can provide biocompatibility and are emerging candidates for templating organic optoelectronics. Silver (Ag) in its nanoscale form shows excellent optical properties. Herein, we combine both materials using thin-film large-area spray-coating to study the fabrication of optical response applications. We characterize the Ag nanoparticle formation by X-ray scattering and UV-vis spectroscopy in situ during growth on the nanocellulose template. The morphology and optical properties of the nanocellulose film are compared to the rigid reference surface SiO2. Our results clearly show the potential to tailor the energy band gap of the resulting hybrid material., QC 20210802

Polymer-metal composite films with nanostructured metal and/or polymer interfaces show a significant perspective for optoelectronic applications, for example, as sensors or in organic photovoltaics (OPVs). The polymer components used in these devices are mostly nanostructured conductive polymers with conjugated pi-electron systems. Enhanced OPV's power conversion efficiencies or sensor sensitivity can be achieved by selective metal deposition on or into polymer templates. In this study, we exploit time-resolved grazing-incidence X-ray scattering to observe the metal-polymer interface formation and the cluster crystallite size in situ during silver (Ag) sputter deposition on a poly(3-hexylthiophene-2,5-diyl)-b-poly(methyl methacrylate) (PMMA-b-P3HT) template. We compare the arising nanoscale morphologies with electronic properties, determine Ag growth regimes, and quantify the selective Ag growth for the diblock copolymer (DBC) template using the corresponding homopolymer thin films (P3HT and PMMA) as a reference. Hence, we are able to describe the influence of the respective polymer blocks and substrate effects on the Ag cluster percolation: the percolation threshold is correlated with the insulator-to-metal transition measured in situ with resistance measurements during the sputter deposition. The Ag cluster percolation on PMMA-b-P3HT starts already on the network of the hexagonal P3HT domain before a complete metal film covers the polymer surface, which is complemented by microscopic measurements. In general, this study demonstrates a possible method for the selective Ag growth as a scaffold for electrode preparation in nanoelectronics and for energy harvesting applications., QC 20210604

The polymerization of a bio-based terpene-derived monomer, sobrerol methacrylate (SobMA), was evaluated in the design of polymeric nanoparticles (nanolatexes). Their synthesis was accomplished by using emulsion polymerization, either by free-radical polymerization in the presence of a cationic surfactant or a cationic macroRAFT agent by employing RAFT-mediated polymerization-induced self-assembly (PISA). By tuning the length of the hydrophobic polymer, it was possible to control the nanoparticle size between 70 and 110 nm. The average size of the latexes in both wet and dry state were investigated by microscopy imaging and dynamic light scattering (DLS). Additionally, SobMA was successfully copolymerized with butyl methacrylate (BMA) targeting soft-core nanolatexes. The comparison of the kinetic profile of the cationically stabilized nanolatexes highlighted the differences of both processes. The SobMA-based nanolatexes yielded high T-g similar to 120 degrees C, while the copolymer sample exhibited a lower T-g similar to 50 degrees C, as assessed by Differential Scanning Calorimetry (DSC). Thereafter, the nanolatexes were adsorbed onto cellulose (filter paper), where they were annealed at elevated temperatures to result in polymeric coatings. Their morphologies were analysed by Field Emission Scanning Electron Microscopy (FE-SEM) and compared to a commercial sulfate polystyrene latex (PS latex). By microscopic investigation the film formation mechanism could be unravelled. Water contact angle (CA) measurements verified the transition from a hydrophilic to a hydrophobic surface after film formation had occured. The obtained results are promising for the toolbox of bio-based building blocks, focused on sobrerol-based monomers, to be used in emulsion polymerizations either for tailored PISA-latexes or facile conventional latex formation, in order to replace methyl methacrylate or other high T-g-monomers., QC 20210409

Spray deposition is a scalable and cost-effective technique for the fabrication of magnetic hybrid films containing diblock copolymers (DBCs) and magnetic nanoparticles. However, it is challenging to obtain spray-deposited anisotropic magnetic hybrid films without using external magnetic fields. In the present work, spray deposition is applied to prepare perpendicular anisotropic magnetic hybrid films by controlling the orientation of strontium hexaferrite nanoplatelets inside ultra-high-molecular-weight DBC polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films. During spray deposition, the evolution of DBC morphology and the orientation of magnetic nanoplatelets are monitored with in situ grazing-incidence small-angle X-ray scattering (GISAXS). For reference, a pure DBC film without nanoplatelets is deposited with the same conditions. Solvent-controlled magnetic properties of the hybrid film are proven with solvent vapor annealing (SVA) applied to the final deposited magnetic films. Obvious changes in the DBC morphology and nanoplatelet localization are observed during SVA. The superconducting quantum interference device data show that ferromagnetic hybrid polymer films with high coercivity can be achieved via spray deposition. The hybrid films show a perpendicular magnetic anisotropy before SVA, which is strongly weakened after SVA. The spray-deposited hybrid films appear highly promising for potential applications in magnetic data storage and sensors., QC 20210323

Photopolymerization is a key enabling technology offering spatial and temporal control to allow for future functional materials to be made to meet societal needs. However, gaining access to robust experimental techniques to describe the evolution of nanoscale morphology in photo-initiated polymeric systems has proven so far to be a challenging task. Here, we show that these physical transformations can be monitored and quantified at the nanoscale in situ and in real-time. It is demonstrated that the initial structural features of the liquid precursors significantly affect the final morphology and the physical properties of the resulting solid via the occurrence of local heterogeneities in the molecular mobility during the curing transformation. We have made visible how local physical arrestings in the liquid, associated with both cross-linking and vitrification, determine the length scale of the local heterogeneities forming upon curing, found to be in the 10-200nm range. Acomplete account of the structural evolution occurring during photopolymerisation is lacking. Here the physical changes occurring on the nanometer scale during photopolymerisation of acrylates are followed over time by FTIR, X-ray reflectometry, AFM, and GISAXS, offering insight into the mechanism by which initial composition influences the final morphology., QC 20200909

Latex colloids are among the most promising materials for broad thin film applications due to their facile surface functionalization. Yet, the effect of these colloids on chemical film and wetting properties cannot be easily evaluated. At the nanoscale, core–shell particles can deform and coalesce during thermal annealing, yielding fine-tuned physical properties. Two different core–shell systems (soft and rigid) with identical shells but with chemically different core polymers and core sizes are investigated. The core–shell nanoparticles (NPs) are probed during thermal annealing in order to investigate their behavior as a function of nanostructure size and rigidity. X-ray scattering allows to follow the re-arrangement of the NPs and the structural evolution in situ during annealing. Evaluation by real-space imaging techniques reveals a disappearance of the structural integrity and a loss of NP boundaries. The possibility to fine-tune the wettability by tuning the core–shell NPs morphology in thin films provides a facile template methodology for repellent surfaces., QC 20200630

Conjugated polymers are regarded as promising candidates for dopant-free hole-transport materials (HTMs) in efficient and stable perovskite solar cells (PSCs). Thus far, the vast majority of polymeric HTMs feature structurally complicated benzo[1,2-b:4,5-b']dithiophene (BDT) analogs and electron-withdrawing heterocycles, forming a strong donor-acceptor (D-A) structure. Herein, a new class of phenanthrocarbazole (PC)-based polymeric HTMs (PC1, PC2, and PC3) has been synthesized by inserting a PC unit into a polymeric thiophene or selenophene chain with the aim of enhancing the pi-pi stacking of adjacent polymer chains and also to efficiently interact with the perovskite surface through the broad and planar conjugated backbone of the PC. Suitable energy levels, excellent thermostability, and humidity resistivity together with remarkable photoelectric properties are obtained via meticulously tuning the conformation and elemental composition of the polymers. As a result, PSCs containing PC3 as dopant-free HTM show a stabilized power conversion efficiency (PCE) of 20.8% and significantly enhanced longevity, rendering one of the best types of PSCs based on dopant-free HTMs. Subsequent experimental and theoretical studies reveal that the planar conformation of the polymers contributes to an ordered and face-on stacking of the polymer chains. Furthermore, introduction of the "Lewis soft" selenium atom can passivate surface trap sites of perovskite films by Pb-Se interaction and facilitate the interfacial charge separation significantly. This work reveals the guiding principles for rational design of dopant-free polymeric HTMs and also inspires rational exploration of small molecular HTMs., QC 20201110

The need for renewable alternatives for fossil-based aromatic material constituents is evident for a more sustainable society. Lignin is the largest source of naturally occurring aromatic compounds but has mainly been considered as waste material or energy source in the pulp and paper industry. Developments in extracting lignin from these processes provide a large source for renewable aromatic structures to be used in various applications. Producing thermosets out of lignin is a very promising route to utilize this raw material toward, for example, composite application. The buildup of the molecular network based on oligomeric lignin segments will be different from traditional thermoset analogues, where the constituents often are smaller molecules, and will have an effect on the material properties. In this work LignoBoost Kraft lignin is refined, chemically modified, and used to produce freestanding thermosets with different architectures and properties. These different thermosets are evaluated, and the possibilities to tailor the material properties through work-up and modification are demonstrated. Morphological studies on the formed thermosets using X-ray scattering show systematic differences in molecular stacking and aggregate sizes., QC 20200331

Many nanoscale biopolymer building blocks with defect-free molecular structure and exceptional mechanical properties have the potential to surpass the performance of existing fossil-based materials with respect to barrier properties, load-bearing substrates for advanced functionalities, as well as light-weight construction. Comprehension and control of performance variations of macroscopic biopolymer materials caused by humidity-driven structural changes at the nanoscale are imperative and challenging. A long-lasting challenge is the interaction with water molecules causing reversible changes in the intrinsic molecular structures that adversely affects the macroscale performance. Using in situ advanced X-ray and neutron scattering techniques, we reveal the structural rearrangements at the nanoscale in ultrathin nanocellulose films with humidity variations. These reversible rearrangements are then correlated with wettability that can be tuned. The results and methodology have general implications not only on the performance of cellulose-based materials but also for hierarchical materials fabricated with other organic and inorganic moisture-sensitive building blocks., QC 20200916

Perovskite solar cells (PSCs) has skyrocketed in the past decade to an unprecedented level due to their outstanding photoelectric properties and facile processability. However, the utilization of expensive hole transport materials (HTMs) and the inevitable instability instigated by the deliquescent dopants represent major concerns hindering further commercialization. Here, a series of low-cost, conjugated polymers are designed and applied as dopant-free HTMs in PSCs, featuring tuned energy levels, good temperature and humidity resistivity, and excellent photoelectric properties. Further studies highlight the critical and multifaceted roles of the polymers with respect to facilitating charge separation, passivating the surface trap sites of perovskite materials, and guaranteeing long-term stability of the devices. A stabilized power conversion efficiency (PCE) of 20.3% and remarkably enhanced device longevity are achieved using the dopant-free polymer P3 with a low concentration of 5 mg/mL, qualifying the device as one of the best PSC systems constructed on the basis of dopant-free HTMs so far. In addition, the flexible PSCs based on P3 also exhibit a PCE of 16.2%. This work demonstrates a promising route toward commercially viable, stable, and efficient PSCs., QC 20220503

QC 20190919

QC 20190918

Mesoporous titania films with tailored nanostructures are fabricated via slot-die printing, which is a simple and cost-effective thin-film deposition technique with the possibility of a large-scale manufacturing. Based on this technique, which is favorable in industry, TiO2 films possess the similar advantage with polymer semiconducting devices like ease of large-scale production. The titania morphologies, including foam-like nanostructures, nanowire aggregates, collapsed vesicles and nanogranules, are achieved via a so-called block-copolymer-assisted sol-gel synthesis. By adjusting the weight fraction of reactants, the ternary morphology phase diagram of the printed titania films is probed after template removal. The surface and inner morphology evolutions are explored with scanning electron microscopy and grazing incidence small-angle X-ray scattering, respectively. Special focus is set on foam-like titania nanostructures as they are of especial interest for, e.g., solar cell applications. At a low weight fraction of the titania precursor titanium(IV)isopropoxide (TTIP), foam-like titania films are achieved, which exhibit a high uniformity and possess large pore sizes. The anatase phase of the highly crystalline titania films is verified with X-ray diffraction and transmission electron microscopy., QC 20191105

Tailoring the optical and electronic properties of nanostructured polymer-metal composites demonstrates great potential for efficient fabrication of modern organic optical and electronic devices such as flexible sensors, transistors, diodes, or photovoltaics. Self-assembled polymer metal nanocomposites offer an excellent perspective for creating hierarchical nanostructures on macroscopic scales by simple bottom-up processes. We investigate the growth processes of nanogranular silver (Ag) layers on diblock copolymer thin film templates during sputter deposition. The Ag growth is strongly driven by self-assembly and selective wetting on the lamella structure of polystyrene-block-poly (methyl methacrylate). We correlate the emerging nanoscale morphologies with collective optical and electronic properties and quantify the difference in Ag growth on the corresponding homopolymer thin films. Thus, we are able to determine the influence of the respective polymer template and observe substrate effects on the Ag cluster percolation threshold, which affects the insulator-to-metal transition (IMT). Optical spectroscopy in the UV-vis regime reveals localized surface plasmon resonance for the metal polymer composite. Their maximum absorption is observed around the IMT due to the subsequent long-range electron conduction in percolated nanogranular Ag layers. Using X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy, we identify the oxidation of Ag at the acrylate side chains as an essential influencing factor driving the selective wetting behavior in the early growth stages. The results of polymer-templated cluster growth are corroborated by atomic force microscopy and field emission scanning electron microscopy., QC 20190912