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At least 55 records · Page 3

Polymer-assisted deposition of nanoparticle feedstocks for target fabrication

Traditional polymer-assisted deposition has been shown to produce highly uniform thin films of metal oxides, including actinide oxides. Furthermore, while producing thicker films for nuclear targets is possible through repeated coating application, we exchanged the dissolved metal species with nanoparticles to maximize the thickness that can be achieved with an individual layer. Using CeO 2 nanoparticles in a polyethyleneimine matrix, we produced targets with single-layer areal densities of 0.22 ± 0.01 mg·cm −2 (1σ) and thicknesses of 690 ± 80 nm (1σ). A custom 3D-printed spin coating chuck attachment with an inlay improved target homogeneity and will streamline future work with radioactive materials.

and nuclear chemistry↗

Scalable fabrication and coating methods for perovskite solar cells and solar modules

Since the report in 2012 of a solid-state perovskite solar cell (PSC) with a power-conversion efficiency (PCE) of 9.7% and a stability of 500 h, intensive efforts have been made to increase the certified PCE, reaching 25.2% in 2019. The PCE of PSCs now exceeds that of conventional thin-film solar-cell technologies, and the rate at which this increase has been achieved is unprecedented in the history of photovoltaics. Moreover, the development of moisture-stable and heat-stable materials has increased the stability of PSCs. Small-area devices (<1 cm2) are typically fabricated using a spin-coating method; however, this approach may not be suitable for the preparation of the large-area (>100 cm2) substrates required for commercialization. Thus, materials and methods need to be developed for coating large-area PSCs. In this Review, we discuss solution-based and vapour-phase coating methods for the fabrication of large-area perovskite films, examine the progress in performance and the parameters affecting the properties of large-area coatings, and provide an overview of the methodologies for achieving high-efficiency perovskite solar modules.

14 SOLAR ENERGY↗

Achieving High Alignment of Conjugated Polymers by Controlled Dip-Coating

Realizing high polymer chain orientation and ordered thin-film microstructures is beneficial for efficient charge transport of conjugated polymers. However, achieving a high alignment degree remains a challenge due to the sensitive nature of polymers to the processing conditions. By simply varying concentrations during a dip-coating method, the component of polymer aggregates that adopt the planar backbones is enlarged and the ensuing assembly process is promoted. Herein, highly oriented polymer thin films of an isoindigo-based conjugated polymer (PII-2T) are prepared to enhance polymer orientation resulting in a drastic booming in carrier mobilities of organic field-effect-transistors (OFETs). The maximum mobility from aligned polymer films increases by up to 8.3 cm 2 V -1 s -1 , which is tenfold beyond the value evaluated from the unaligned direction or traditional spin-coated samples. The enhanced orientation can also reduce the adverse effects of the contact resistance and facilitate charge transport in transistors. This work demonstrates that the highly aligned conjugated polymer films can be approached by the dip-coating method while offers a latent cornerstone toward understanding the critical role of processing-related parameters in determining morphology of solution-coated thin films.

36 MATERIALS SCIENCE↗

Developing Efficient Perovskite/Silicon Tandem Devices

This project aims at developing highly efficient perovskite/silicon tandem solar cells by developing efficient perovskite top cells, silicon bottom cells, and monolithically integrating the subcells for highly efficient tandem solar cells. The project focused on increasing the efficiency of perovskite solar cells to 20% and understanding related materials science and device physics, as well as developing a compatible bottom high-efficiency c-Si solar cell. The perovskite cells with a wide bandgap of 1.61 eV and 1.84 eV are fabricated by a low-cost, low-temperature, scalable solution process on lower bandgap silicon bottom cells. The bandgaps of perovskite top cells have been tuned between 1.61 eV and 1.84 eV by composition engineering mainly through controlling the halide mixing ratio in perovskite materials. The efficiencies of the wide bandgap perovskite solar cells have been improved to an excellent efficiency of 21.0% for perovskites with a bandgap of 1.63 eV with increased grain size, reduced energy disorder at cathode contact, and defect passivation. We invented a solvent annealing approach with solvent vapor during thermal annealing to enlarge grain size of perovskite film which reduces the charge trap density and improves the device efficiency. Moreover, we discovered that the non-wetting surface could further increase the grain size for perovskite films, because non-wetting surface could prevent the formation of too dense nuclei from heterogeneous nucleation process. We proposed to reduce the energy disorder of organic charge extraction layer to reduce the power loss in perovskite cells. We pioneered defect passivation concept and techniques to suppress the charge non-radiative recombination in perovskite solar cells to boost the efficiency. For the silicon bottom cell development, different from the conventional silicon cell work under full illumination, the light available for the silicon bottom cell in tandem structure is mainly NIR region. We developed a NIR enhanced silicon cell with efficiency of 21.2% by applying a double-layer antireflection coating at the front side and a MgF2 back reflector layer at the rear side. For the perovskite/silicon tandem device, we achieved a highest reported power conversion efficiency of 25.4% in 2018, and further increased the efficiency up to 26.0% in 2019. The research on tandem solar cells focused on reducing reflection loss to <5% at spectrum of 300-1100 nm by antireflection layer, tuning the bandgap of perovskite film for matched current density between sub-cells, and utilizing a ITO layer between perovskite top cell and silicon bottom cell as interconnect layer without Voc loss. Finally, we developed a blading technique to fabricate perovskite films which produces perovskite solar cells with comparable or even superior efficiency to those made by non-scalable spin coating method. This paves the way for scaling up perovskite/silicon tandem solar cells using solution approach.

14 SOLAR ENERGY↗

Ferromagnetic resonators synthesized by metal-organic decomposition epitaxy

Abstract Metal-organic decomposition epitaxy is an economical wet-chemical approach suitable to synthesize high-quality low-spin-damping films for resonator and oscillator applications. This work reports the temperature dependence of ferromagnetic resonances and associated structural and magnetic quantities of yttrium iron garnet nanofilms that coincide with single-crystal values. Despite imperfections originating from wet-chemical deposition and spin coating, the quality factor for out-of-plane and in-plane resonances approaches 600 and 1000, respectively, at room temperature and 40 GHz. These values increase with temperature and are 100 times larger than those offered by commercial devices based on complementary metal-oxide semiconductor voltage-controlled oscillators at comparable production costs.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural Asymmetry and Chiral-Induced Spin Selectivity in Chiral Palladium-Halide Semiconductors

Chiral Pb-free metal-halide semiconductors (MHSs) have attracted considerable attention in the field of spintronics due to various interesting spin-related properties and chiral-induced spin selectivity (CISS) effect. Despite their excellent chemical and structural tunability, the material scope and crystal structure of Pb-free chiral MHSs exhibiting the CISS effect are still limited; chiral MHSs that have metal-halide structures of octahedra and tetrahedra are only reported. Here, we report a new class of chiral MHSs, of which palladium (Pd)-halides are formed in 1D square-pyramidal structures or 0D square-planar structures, with a general formula of ((R/S-MBA) 2 PdBr 4 ) 1-x ((R/S-MBA) 2 PdCl 4 ) x (MBA = methylbenzylammonium; x = 0, 0.25, 0.5, 0.75, and 1) for the first time. The crystals adopt the 1D helical chain of Pd-halide square-pyramid (for x = 0, 0.25, 0.5, and 0.75) and 0D structure of Pd-halide square-plane (for x = 1). All the Pd-halides are distorted by the interaction between the halide and the chiral organic ammonium and arranged in a noncentrosymmetric position. Circular dichroism (CD) for ((R/S-MBA) 2 PdBr 4 ) 1-x ((R/S-MBA) 2 PdCl 4 ) x indicates that chirality was transferred from chiral organic ammonium to Pd-halide inorganics. ((R-MBA) 2 PdBr 4 ) 1-x ((R-MBA) 2 PdCl 4 ) x (x = 0, 0.25, 0.5, and 0.75) shows a distortion index of 0.127-0.128, which is the highest value among the previously reported chiral MHSs to the best of our knowledge. We also find that (R/S-MBA) 2 Pd(Br 1-x Cl x ) 4 crystals grow along the out-of-plane direction during spin coating and have high c-axis orientation and crystallinity, and (R/S-MBA) 2 Pd(Br 1-x Cl x ) 4 (x = 0 and 0.5) crystals exhibit a CISS effect in polycrystalline bulk films. In conclusion, these results demonstrate the possibility of a new metal-halide series with square-planar structures or square-pyramidal structures for future spintronic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

All Electrospray Printing of Carbon–Based Cost–Effective Perovskite Solar Cells

With the power conversion efficiencies of PSCs exceeding 25%, the perovskite solar cells (PSCs) are closer to step into the initial industrialization. Prior to transferring from laboratory fabrication to industrial manufacturing, issues such as scalability, materials cost, and production line compatibility that significantly impact the manufacturing remain to be addressed. Here we report breakthroughs on all these fronts. Carbon-based PSCs with architecture FTO/electron transport layer/perovskite/carbon, that eliminate the need for the hole transport layer and noble metal electrode, provide ultra-low-cost configuration. This PSC architecture was manufactured using a scalable and industrially compatible electrospray (ES) technique, which enables continuous printing of all the cell layers. The ES deposited electron transport layer and perovskite layer exhibited properties comparable to that of the laboratory-scale spin coating method. The ES deposited carbon electrode layer exhibited superior conductivity and interfacial microstructure in comparison to films synthesized using the conventional doctor blading technique. As a result, the fully ES printed carbon-based PSCs showed a record 14.41% power conversion efficiency, rivaling the state-of-the-art hole transporter-free PSCs. Furthermore, these results will immediately have an impact on the scalable production of PSCs.

14 SOLAR ENERGY↗

Unravelling the Role of Electron Acceptors for the Universal Enhancement of Charge Transport in Quinoid-Donor-Acceptor Polymers for High-Performance Transistors

The quinoid-donor-acceptor (Q-D-A) strategy has recently emerged as a promising approach for constructing high mobility semiconducting polymers. In order to fully explore the potential of this strategy in improving the charge transport and elucidating the structure-property-performance relationships in Q-D-A polymers, a series of new polymers with different electron acceptor units and backbone coplanarity have been synthesized and characterized. In this work, all of the resulting Q-D-A polymers exhibit much more planar backbone conformations in comparison to their donor-acceptor (D-A) counterparts. Moreover, organic field-effect transistors based on Q-D-A polymers exhibit excellent effective hole mobilities in a range of 0.44 to 3.35 cm 2 V –1 s –1 , most of which are orders of magnitude higher than those of their corresponding D-A polymers. Notably, the hole mobility of 3.35 cm 2 V –1 s –1 is among the highest for the quinoidal-aromatic polymers characterized by conventional spin-coating methods. Furthermore, the role of electron acceptors in Q-D-A polymers has been comprehensively investigated. Polymers with stronger acceptor units are more inclined to deliver edge-on lamellas, high film crystallinity, small effective hole masses, and decent operational stability. The detailed structure-property-device performance relationship will pave the way toward high performance semiconducting polymers using the potent Q-D-A strategy.

36 MATERIALS SCIENCE↗

High‐Performance Green Thick‐Film Ternary Organic Solar Cells Enabled by Crystallinity Regulation

Abstract The power conversion efficiency (PCE) of organic solar cells (OSCs) has reached high values of over 19%. However, most of the high‐efficiency OSCs are fabricated by spin‐coating with toxic solvents and the optimal photoactive layer thickness is limited to 100 nm, limiting practical development of OSCs. It is a great challenge to obtain ideal morphology for high‐efficiency thick‐film OSCs when using non‐halogenated solvents due to the unfavorable film formation kinetics. Herein, high‐efficiency ternary thick‐film (300 nm) OSCs with PCE of 15.4% based on PM6:BTR‐Cl:CH1007 are fabricated by hot slot‐die coating using non‐halogenated solvent (o‐xylene) in the air. Compared to PM6:BTR‐Cl:Y6 blends, the stronger pre‐aggregation of CH1007 in solution induces the earlier aggregation of CH1007 molecules and longer aggregation time, and thus results in high and balanced crystallinity of donors and acceptor in CH1007‐based ternary film, which led to high‐carrier mobility and suppressed charge recombination. The ternary strategy is further used to fabricate high‐efficiency, thick‐film, large‐area, and flexible devices processed from non‐halogenated solvents, paving the way for industrial development of OSCs.

Chemistry↗

Influence of Methylammonium Chloride on Wide-Bandgap Halide Perovskites Films for Solar Cells

Wide-bandgap perovskites are of paramount importance as the photoactive layer of the top cell in high-efficiency tandem solar cells. Comparably high Br contents are required to widen the perovskite bandgap. However, the increase in Br content causes heterogeneous halide distribution and photoinstability. Here, in this study, the positive effect of the additive methylammonium chloride (MACl) on the optical and electronic properties of Br-rich perovskite, deposited using N-methyl-2-pyrrolidone (NMP) as co-solvent and the gas quenching method, is investigated. Simultaneous in situ grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy are used to track the evolution of the structural and optoelectronic properties of the perovskites with different amounts of Br and MACl during the spin-coating and thermal annealing steps. The formation mechanism is elucidated in the presence of MACl. It is observed that chloride ions inhibit the intermediate phases, favoring the formation of a perovskite phase with higher crystallinity. Nano X-ray fluorescence mapping recognizes Br-richer and poorer nanometric domains, whose average sizes reduce for samples with MACl. In conclusion, it is demonstrated that adding MACl affects the formation of wide-bandgap perovskites via destabilization of the intermediate phases and acts on the homogenization of the halide distribution, leading to improved solar cell performances.

14 SOLAR ENERGY↗

Assembly of Close–Packed Ferroelectric Polymer Nanowires via Interface–Epitaxy with ReS 2

The flexible, transparent, and low-weight nature of ferroelectric polymers makes them promising for wearable electronic and optical applications. To reach the full potential of the polarization-enabled device functionalities, large-scale fabrication of polymer thin films with well-controlled polar directions is called for, which remains a central challenge. The widely exploited Langmuir–Blodgett, spin-coating, and electrospinning methods only yield polymorphous or polycrystalline films, where the net polarization is compromised. Here, an easily scalable approach is reported to achieve poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) thin films composed of close-packed crystalline nanowires via interface-epitaxy with 1T'-ReS 2 . Upon controlled thermal treatment, uniform P(VDF-TrFE) films restructure into about 10 and 35 nm-wide (010)-oriented nanowires that are crystallographically aligned with the underlying ReS 2 , as revealed by high-resolution transmission electron microscopy. Piezoresponse force microscopy studies confirm the out-of-plane polar axis of the nanowire films and reveal coercive voltages as low as 0.1 V. Reversing the polarization can induce a conductance switching ratio of >10 8 in bilayer ReS 2 , over six orders of magnitude higher than that achieved by an untreated polymer gate. Lastly, this study points to a cost-effective route to large-scale processing of high-performance ferroelectric polymer thin films for flexible energy-efficient nanoelectronics.

crystalline nanowires↗

Hot-Casting-Assisted Liquid Additive Engineering for Efficient and Stable Perovskite Solar Cells

High-performance inorganic–organic lead halide perovskite solar cells (PSCs) are often fabricated with a liquid additive such as dimethyl sulfoxide (DMSO), which retards crystallization and reduces roughness and pinholes in the perovskite layers. However, DMSO can be trapped during perovskite film formation and induce voids and undesired reaction byproducts upon later processing steps. Here, it is shown that the amount of residual DMSO can be reduced in as-spin-coated films significantly through use of preheated substrates, or a so-called hot-casting method. Hot casting increases the perovskite film thickness given the same concentration of solutions, which allows for reducing the perovskite solution concentration. By reducing the amount of DMSO in proportion to the concentration of perovskite precursors and using hot casting, it is possible to fabricate perovskite layers with improved perovskite–substrate interfaces by suppressing the formation of byproducts, which increase trap density and accelerate degradation of the perovskite layers. The best-performing PSCs exhibit a power conversion efficiency (PCE) of 23.4% (23.0% stabilized efficiency) under simulated solar illumination. Furthermore, encapsulated devices show considerably reduced post-burn-in decay, retaining 75% and 90% of their initial and post-burn-in efficiencies after 3000 h of operation with maximum power point tracking (MPPT) under high power of ultraviolet (UV)-containing continuous light exposure.

perovskite-substrate interface↗

Strong Induced Circular Dichroism in a Hybrid Lead‐Halide Semiconductor Using Chiral Amino Acids for Crystallite Surface Functionalization

Abstract Chirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically‐pure 3‐aminobutyric acid (3‐ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI 3 ) is found to result in strong circular dichroism (CD) in the optical absorption. X‐ray diffraction and grazing incidence small angle X‐ray scattering (GISAXS) are applied to gain molecular‐scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI 3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino‐acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin‐coating time, thereby achieving anisotropy factors ( g abs ) as high as 1.75 × 10 –2 . Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters.

36 MATERIALS SCIENCE↗

One‐Step Thermal Gradient‐ and Antisolvent‐Free Crystallization of All‐Inorganic Perovskites for Highly Efficient and Thermally Stable Solar Cells

Abstract All‐inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat‐sensitive hybrid organic–inorganic counterparts. In particular, CsPbI 2 Br shows the highest potential for developing thermally‐stable perovskite solar cells (PSCs) among all‐inorganic compositions. However, controlling the crystallinity and morphology of all‐inorganic compositions is a significant challenge. Here, a simple, thermal gradient‐ and antisolvent‐free method is reported to control the crystallization of CsPbI 2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin‐coating and annealing to understand and optimize the evolving film properties. This leads to high‐quality perovskite films with micrometer‐scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open‐circuit voltage ( V OC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.

36 MATERIALS SCIENCE↗

A Three-in-One Hybrid Strategy for High-Performance Semiconducting Polymers Processed from Anisole

The development of semiconducting polymers with good processability in green solvents and competitive electrical performance is essential for realizing sustainable large-scale manufacturing and commercialization of organic electronics. A major obstacle is the processability-performance dichotomy that is dictated by the lack of ideal building blocks with balanced polarity, solubility, electronic structures, and molecular conformation. Herein, through the integration of donor, quinoid and acceptor units, an unprecedented building block, namely TQBT, is introduced for constructing a serial of conjugated polymers. The TQBT, distinct in non-symmetric structure and high dipole moment, imparts enhanced solubility in anisole—a green solvent—to the polymer TQBT-T. Furthermore, PTQBT-T possess a highly rigid and planar backbone owing to the nearly coplanar geometry and quinoidal nature of TQBT, resulting in strong aggregation in solution and localized aggregates in film. Remarkably, PTQBT-T films spuncast from anisole exhibit a hole mobility of 2.30 cm 2 V -1 s -1 , which is record high for green solvent-processable semiconducting polymers via spin-coating, together with commendable operational and storage stability. The hybrid building block emerges as a pioneering electroactive unit, shedding light on future design strategies in high-performance semiconducting polymers compatible with green processing and marking a significant stride towards ecofriendly organic electronics.

36 MATERIALS SCIENCE↗

Revealing the Transient Formation Dynamics and Optoelectronic Properties of 2D Ruddlesden–Popper Phases on 3D Perovskites

Using in situ photoluminescence measurements during the spin-coating and annealing steps, this study probes the formation of 2D layers on 3D triple cation perovskite films comparing phenylethylammonium and 2-thiophenemethylammonium iodide bulky cations. This study elucidates the formation mechanisms of the surface layers for both cases and reveals two regimes during 2D layer formation: a kinetic-driven and a thermodynamic-driven process. These driving forces result in different compositions of the 2D/3D interface for each treatment, namely, different ratios of pure 2D (n = 1) and quasi-2D (n > 1) structures. Further, this study shows that a higher ratio of quasi-2D phases is more beneficial for device performance, as pure-2D layers may hamper current extraction. Due to a more evenly distributed formation energy profile among 2D and quasi-2D phases, highly concentrated 2-thiophenemethylammonium iodide appears to be more suited for effective surface passivation than its phenylethylammonium analog.

36 MATERIALS SCIENCE↗

Alumina – Stabilized SEI and CEI in Potassium Metal Batteries

Aluminum oxide (Al 2 O 3 ) nanopowder is spin-coated onto both sides of commercial polypropene separator to create artificial solid-electrolyte interphase (SEI) and artificial cathode electrolyte interface (CEI) in potassium metal batteries (KMBs). Here, this significantly enhances the stability, including of KMBs with Prussian Blue (PB) cathodes. For example, symmetric cells are stable after 1,000 cycles at 0.5 mA/cm 2 –0.5 mAh/cm 2 and 3.0 mA/cm 2 –0.5 mAh/cm 2 . Alumina modified separators promote electrolyte wetting and increase ionic conductivity (0.59 vs. 0.2 mS/cm) and transference number (0.81 vs. 0.23). Cryo-stage focused ion beam (cryo-FIB) analysis of cycled modified anode demonstrates dense and planar electrodeposits, versus unmodified baseline consisting of metal filaments (dendrites) interspersed with pores and SEI. Alumina-modified CEI also suppresses elemental Fe crossover and reduces cathode cracking. Mesoscale modeling of metal – SEI interactions captures crucial role of intrinsic heterogeneities, illustrating how artificial SEI affects reaction current distribution, conductivity and morphological stability.

25 ENERGY STORAGE↗

Sustainable Production of Biomass‐Derived Graphite and Graphene Conductive Inks from Biochar

Abstract Graphite is a commonly used raw material across many industries and the demand for high‐quality graphite has been increasing in recent years, especially as a primary component for lithium‐ion batteries. However, graphite production is currently limited by production shortages, uneven geographical distribution, and significant environmental impacts incurred from conventional processing. Here, an efficient method of synthesizing biomass‐derived graphite from biochar is presented as a sustainable alternative to natural and synthetic graphite. The resulting bio‐graphite equals or exceeds quantitative quality metrics of spheroidized natural graphite, achieving a RamanI D /I G ratio of 0.051 and crystallite size parallel to the graphene layers (L a ) of 2.08 µm. This bio‐graphite is directly applied as a raw input to liquid‐phase exfoliation of graphene for the scalable production of conductive inks. The spin‐coated films from the bio‐graphene ink exhibit the highest conductivity among all biomass‐derived graphene or carbon materials, reaching 3.58 ± 0.16 × 10 4 S m −1 . Life cycle assessment demonstrates that this bio‐graphite requires less fossil fuel and produces reduced greenhouse gas emissions compared to incumbent methods for natural, synthesized, and other bio‐derived graphitic materials. This work thus offers a sustainable, locally adaptable solution for producing state‐of‐the‐art graphite that is suitable for bio‐graphene and other high‐value products.

Chemistry↗