Manipulation of Crystal Orientation and Phase Distribution of Quasi-2D Perovskite through Synergistic Effect of Additive Doping and Spacer Engineering.

The diammonium precursor 1,4-phenylenedimethanammonium (PDMA) was used as a large organic spacer for the preparation of Dion-Jacobson-type quasi-2D perovskites (PDMA)(MA)n-1PbnI3n+1 (MA = methylammonium). Films with composition ⟨n⟩ = 5 comprised randomly orientated grains and multiple microstructural domains with locally differing n values. However, by mixing the Dion-Jacobson-type spacer PDMA and the Ruddlesden-Popper-type spacer propylammonium (PA), the crystal orientation in both the vertical and the horizonal directions became regulated. High crystallinity owing to well-matched interlayer distances was observed. Combining this spacer-engineering approach with the addition of methylammonium chloride (MACl) led to full vertical alignment of the crystal orientation. Moreover, the microstructural domains at the substrate interface changed from low-n (n = 1, 2, 3) to high-n (n = 4, 5), which may be beneficial for hole extraction at the interface between perovskite and hole transport layer due to a more finely tuned band alignment. Our work sheds light on manipulating the crystallization behavior of quasi-2D perovskite and further paves the way for highly stable and efficient perovskite devices.

Metal Oxide Nanosheets as 2D Building Blocks for the Design of Novel Materials.

Research into 2-dimensional materials has soared during the last couple of years. Next to van der Waals type 2D materials such as graphene and h-BN, less well-known oxidic 2D equivalents also exist. Most 2D oxide nanosheets are derived from layered metal oxide phases, although few 2D oxide phases can be also made by bottom-up solution syntheses. Owing to the strong electrostatic interactions within layered metal oxide crystals, a chemical process is usually needed to delaminate them into their 2D constituents. This Review article provides an overview of the synthesis of oxide nanosheets, and methods to assemble them into nanocomposites, mono- or multilayer films. In particular, the use of Langmuir-Blodgett methods to form monolayer films over large surface areas, and the emerging use of ink jet printing to form patterned functional films is emphasized. The utilization of nanosheets in various areas of technology, for example, electronics, energy storage and tribology, is illustrated, with special focus on their use as seed layers for epitaxial growth of thin films, and as electrochemically active electrodes for supercapacitors and Li ion batteries.

Following the Kinetics of Barium Titanate Nanocrystal Formation in Benzyl Alcohol Under Near-Ambient Conditions.

In complex chemical syntheses (e.g., coprecipitation reactions), nucleation, growth, and coarsening often occur concurrently, obscuring the individual processes. Improved knowledge of these processes will help to better understand and optimize the reaction protocol. Here, a form-free and model independent approach, based on a combination of time-resolved small/wide-angle X-ray scattering, is employed to elucidate the effect of reaction parameters (such as precursor concentration, reactant stoichiometry, and temperature) on the nucleation, crystallization, and growth phenomena during the formation of nanocrystalline barium titanate. The strength of this approach is that it relies solely on the total scattered intensity (i.e., scattering invariant) of the investigated system, and no prior knowledge is required. As such, it can be widely applied to other synthesis protocols and material's systems. Through the scattering invariant, it is found that the amorphous-to-crystalline transformation of barium titanate is predominantly determined by the total amount of water released from the gel-like barium hydroxide octahydrate precursor, and three rate-limiting regimes are established. As a result of this improved understanding of the effect of varying reaction conditions, elementary boundary conditions can be set up for a better control of the barium titanate nanocrystal synthesis.

Influence of Monomer Connectivity, Network Flexibility, and Hydrophobicity on the Hydrothermal Stability of Organosilicas.

It is generally assumed that the hydrothermal stability of organically modified silica networks is promoted by high monomer connectivity, network flexibility, and the presence of hydrophobic groups in the network. In this study a range of organosilica compositions is synthesized to explore the extent to which these factors play a role in the hydrothermal dissolution of these materials. Compositions were synthesized from hexafunctional organically bridged silsesquioxanes (OR1)3Si-R-Si(OR1)3 (R = -CH2-, -C2H4-, -C6H12-, -C8H16-, -p-C6H4-; R1 = -CH3, -C2H5), tetrafunctional (OEt)2Si(CH3)-C2H4-Si(CH3)(OEt)2 and Si(OEt)4, trifunctional silsesquioxanes R'-Si(OMe)3 (R'=CH3, n-C3H7, cyclo-C6H11, phenyl), and bifunctional Si(i-C3H7)2(OMe)2. The bond strain, connectivity and hydroxyl concentration of all networks were estimated using 29Si cross-polarized magic angle spinning nuclear magnetic resonance and Fourier-transform infrared spectroscopy. The hydrophilicity was characterized by monitoring the water uptake of the materials in moisture treatments with thermogravimetric analysis, differential scanning calorimetry, and Fourier-transform infrared spectroscopy. The resistance of each network against hydrothermal dissolution in a water/1,5-pentanediol mixture at 80 °C and pH 1, 7, and 13 was analyzed with inductively coupled plasma optical emission spectroscopy and X-ray fluorescence. Bond strain appears to significantly increase the tendency to dissolve under hydrothermal conditions. The stabilizing influences of increased connectivity and hydrophobicity were found to be weak.

The Rapid Exfoliation and Subsequent Restacking of Layered Titanates Driven by an Acid-Base Reaction.

Two-dimensional (2D) (hydro)oxide materials, that is, nanosheets, enable the preparation of advanced 2D materials and devices. The general synthesis route of nanosheets involves exfoliating layered metal (hydro)oxide crystals. This exfoliation process is considered to be time-consuming, hindering their industrial-scale production. Based on in situ exfoliation studies on the protonated layered titanate H(1.07)Ti(1.73)O4⋅H2O (HTO), it is now shown that ion intercalation-assisted exfoliation driven by chemical reaction provides a viable and fast route to isolated nanosheets. Contrary to the general expectation, data indicate that direct exfoliation of HTO occurs within seconds after mixing of the reactants, instead of proceeding via a swollen state as previously thought. These findings reveal that ion intercalation-assisted exfoliation driven by chemical reaction is a promising exfoliation route for large-scale synthesis.

Formation of nanocrystalline barium titanate in benzyl alcohol at room temperature.

Nanocrystalline barium titanate (8-10 nm crystallite size) was prepared at temperatures of 23-78 °C through reaction of a modified titanium alkoxide precursor in benzyl alcohol with barium hydroxide octahydrate. The room temperature formation of a perovskite phase from solution is associated with the use of benzyl alcohol as solvent medium. The formation mechanism was elucidated by studying the stability and interaction of each precursor with the solvent and with each other using various experimental characterization techniques. Density functional theory (DFT) computational models which agreed well with our experimental data could explain the formation of the solid phase. The stability of the Ti precursor was enhanced by steric hindrance exerted by phenylmethoxy ligands that originated from the benzyl alcohol solvent. Electron microscopy and X-ray diffraction indicated that the crystallite sizes were independent of the reaction temperature. Crystal growth was inhibited by the stabilizing phenylmethoxy groups present on the surface of the crystallites.

Phase distribution regulation of formamidinium-based quasi-2D perovskites through solution engineering.

Quasi-2D perovskites have attracted attention as potential solar energy absorber materials due to their balanced efficiency and stability and their unique quantum-well structures. In order to facilitate directional excitons and charge carrier transport and preferential energy transfer landscape in photovoltaic thin films, the phase distribution formed by different types of microstructural domains should be regulated. In this work, the Dion-Jacobson-type spacer 1,4-phenylenedimethanammonium (PDMA) was used, and different strategies were pursued to control the phase distribution in formamidinium-based (FA) quasi-2D perovskites based on the composition of (PDMA)FA4Pb5I16. In general, doping with FACl modulated the crystallization kinetics, forming 2D low-n crystals on the top surface or a reversed-gradient phase distribution, depending on whether excess or substitutional doping was employed. Alternatively, mixing with a Ruddlesden-Popper spacer helped bridging to adjacent octahedra in pure PDMA-based perovskites and improved crystallization, while regulating the quantum-well structures to give a normal-gradient phase distribution, where 2D domains resided on the bottom side. By combining FACl doping and spacer mixing, the film showed both a reversed-gradient phase distribution and larger vertically aligned grains. This work contributes to the knowledge of how to manipulate and regulate the phase distribution in FA-based quasi-2D perovskites and further paves the way for fabricating corresponding devices with high efficiency and stability.

Simultaneous Enhancement of Lithium Transfer Kinetics and Structural Stability in Dual-Phase TiO2 Electrodes by Ruthenium Doping.

Dual-phase TiO2 consisting of bronze and anatase phases is an attractive electrode material for fast-charging lithium-ion batteries due to the unique phase boundaries present. However, further enhancement of its lithium storage performance has been hindered by limited knowledge on the impact of cation doping as an efficient modification strategy. Here, the effects of Ru4+ doping on the dual-phase structure and the related lithium storage performance are demonstrated for the first time. Structural analysis reveals that an optimized doping ratio of Ru:Ti = 0.01:0.99 (1-RTO) is vital to maintain the dual-phase configuration because the further increment of Ru4+ fraction would compromise the crystallinity of the bronze phase. Various electrochemical tests and density functional theory calculations indicate that Ru4+ doping in 1-RTO enables more favorable lithium diffusion in the bulk for the bronze phase as compared to the undoped TiO2 (TO) counterpart, while lithium kinetics in the anatase phase are found to remain similar. Furthermore, Ru4+ doping leads to a better cycling stability for 1-RTO-based electrodes with a capacity retention of 82.1% after 1200 cycles at 8 C as compared to only 56.1% for TO-based electrodes. In situ X-ray diffraction reveals a reduced phase separation in the lithiated anatase phase, which is thought to stabilize the dual-phase architecture during extended cycling. The simultaneous enhancement of rate ability and cycling stability of dual-phase TiO2 enabled by Ru4+ doping provides a new strategy toward fast-charging lithium-ion batteries.

Ultrahighly Sensitive Flexible Pressure Sensors with Dual-Mode Response Based on Monolayer Films of Calcium Niobate Nanosheets.

Flexible pressure sensors present enormous potential for applications in health monitoring, human-machine interfacing, and electronic skins (e-skin). However, at the cost of flexibility, the design of flexible pressure sensors has been facing the trade off between high sensitivity and wide sensing range. Herein, we propose a sandwiched structure composed of monolayer films of calcium niobate nanosheets to endow the device with both ultrahigh sensitivity and a wide sensing range. Tunable contact between the two electrodes of the pressure sensor through the gaps in the insulative monolayer film and precise thickness modulation of the monolayer films at the nanoscale result in an ultrahigh sensitivity and wide sensing range of the sensors. By virtue of these two traits, the pressure sensor distinguishes itself with unprecedented performances of ultrahigh sensitivity (6.43 × 104 kPa-1), a wide sensing range (1.94-60.00 kPa), a fast response time (<165 ms), and reliable repeatability. In addition, the sensor has a sensing mechanism transition from capacitive mode to piezoresistive mode from low pressure to high pressure. The sensors demonstrates the ability for motion detection of the human body. This work sheds light on the development of highly sensitive flexible pressure sensors.

Large area resist-free soft lithographic patterning of graphene.

Large area low-cost patterning is a challenging problem in graphene research. A resist-free, single-step, large area and cost effective soft lithographic patterning strategy is presented for graphene. The technique is applicable on any arbitrary substrate that needs to be covered with a graphene film and provides a viable route to large-area patterning of graphene for device applications.

Template-free synthesis of mesoporous and amorphous transition metal phosphate materials.

We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1-x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1-x-struvites exhibit high surface areas and pore volumes (240 m2 g-1 and 0.32 cm-3 g-1 for Mg and 90 m2 g-1 and 0.13 cm-3 g-1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.

Altering the Alkaline Metal Ions in Lepidocrocite-Type Layered Titanate for Sodium-Ion Batteries.

The relatively large ionic radius of the Na ion is one of the primary reasons for the slow diffusion of Na ions compared to that of Li ions in de/intercalation processes in sodium-ion batteries (SIBs). Interlayer expansion of intercalation hosts is one of the effective techniques for facilitating Na-ion diffusion. For most ionic layered compounds, interlayer expansion relies on intercalation of guest ions. It is important to investigate the role of these ions for material development of SIBs. In this study, alkali-metal ions (Li+, Na+, K+, and Cs+) with different sizes were intercalated into lepidocrocite-type layered titanate by a simple ion-exchange technique to achieve interlayer modulation and those were then evaluated as anode materials for SIBs. By controlling the intercalated alkaline ion species, basal spacings of layered titanates (LTs) in the range of 0.68 to 0.85 nm were obtained. Interestingly, the largest interlayer spacing induced by the large size of Cs did not yield the best performance, while the Na intercalated layered titanate (Na-ILT) demonstrated a superior performance with a specific capacity of 153 mAh g-1 at a current density of 0.1 A g-1. We found that the phenomena can be explained by the high alkaline metal ion concentration and the efficient utilization of the active sites in Na-ILT. The detailed analysis indicates that large intercalating ions like Cs can hamper sodium-ion diffusion although the interlayer spacing is large. Our work suggests that adopting an appropriate interlayer ion species is key to developing highly efficient layered electrode materials for SIBs.

Thermally processed Ni-and Co-struvites as functional materials for proton conductivity.

Here, we describe how to synthesise proton-conductive transition metal phosphates (TMPs) by direct thermal processing of precursor M-struvites, NH4MPO4·6H2O, with M = Ni2+, Co2+. In the as-derived TMP phases their thermal history and bulk proton conductivity were linked with the structural information about the metal coordination, phosphate groups, and volatile compounds. These aspects were investigated with vibrational and synchrotron-based spectroscopic methods (FT-IR, FT-RS, XAS). We elucidated the structures of amorphous and crystalline Ni- and Co phosphate phases in association with different coordination changes and distortion degrees of the metal polyhedra as they developed upon heating. Ni-struvite transformed to a stable amorphous phase over a broad range of temperatures (90 °C < T < 600 °C), in which it remained in an octahedral coordination environment, but the degree of distortion changed with T. In contrast, heating of Co-struvite led to several successive crystalline phases with only unstable transitional and short-lived amorphous components. Among the as-occurring phases, a highly functional layered M-dittmarite NH4MPO4·H2O obtained at low temperatures (T < 200 °C) demonstrated high proton conductivity values of 4.2 × 10-5 S cm-1 for Ni-dittmarite and Co-dittmarite > 10-4 S cm-1 at room temperature. Even at low humidity, these values are comparable with those found for Nafion, MOFs, some perovskites or composite materials. Coprecipitation of phosphates and transition metal cations in the form of struvite is potentially a viable method to extract these elements from wastewater. Thus, we propose that recycled M-struvites could be potentially further directly upcycled into crystalline and amorphous TMPs useful for electrochemical applications.

Stabilizing Crystal Framework of an Overlithiated Li1+xMn2O4 Cathode by Heterointerfacial Epitaxial Strain for High-Performance Microbatteries.

To meet the increasing demands of high-energy and high-power-density lithium-ion microbatteries, overlithiated Li1+xMn2O4 (0 ≤ x ≤ 1) is an attractive cathode candidate due to the high theoretical capacity of 296 mAh g-1 and the interconnected lithium-ion diffusion pathways. However, overlithiation triggers the irreversible cubic-tetragonal phase transition due to Jahn-Teller distortion, causing rapid capacity degradation. In contrast to conventional lithium-ion batteries, microbatteries offer the opportunity to develop specific thin-film-based modification strategies. Here, heterointerfacial lattice strain is proposed to stabilize the spinel crystal framework of an overlithiated Li1+xMn2O4 (LMO) cathode by epitaxial thin film growth on an underlying SrRuO3 (SRO) electronic conductor layer. It is demonstrated that the lattice misfit at the LMO/SRO heterointerface results in an in-plane epitaxial constraint in the full LMO film. This suppresses the lattice expansion during overlithiation that typically occurs in the in-plane direction. It is proposed by density functional theory modeling that the epitaxial constraint can accommodate the internal lattice stress originating from the cubic-tetragonal transition during overlithiation. As a result, a doubling of the capacity is achieved by reversibly intercalating a second lithium ion in a LiMn2O4 epitaxial cathode with a complete reversible phase transition. An impressive cycling stability can be obtained with reversible capacity retentions of above 90.3 and 77.4% for the 4 and 3 V range, respectively. This provides an effective strategy toward a stable overlithiated Li1+xMn2O4 epitaxial cathode for high-performance microbatteries.

Disentangling Hot Carrier Decay and the Nature of Low-n to High-n Transfer Processes in Quasi-Two-Dimensional Layered Perovskites.

Quasi-two-dimensional (2D) metal halide perovskites (MHPs) are promising photovoltaic (PV) materials because of their impressive optical and optoelectronic properties and improved stability compared to their 3D counterparts. The presence of domains with varying numbers of inorganic layers between the organic spacers (n-phases), each with different bandgaps, makes the photoinduced carrier dynamics in films of these materials complex and intriguing. Existing interpretations of the ultrafast femto- or picosecond spectroscopy data have been inconsistent, most of them focusing either on exciton/charge transfer from low-n to high-n phases or on hot carrier cooling, but not combined. Here, we present a comprehensive study of the carrier dynamics in the Dion-Jacobson type (PDMA)(MA)(n-1)PbnI(3n+1) (PDMA = 1,4-phenylenedimethylammonium, MA = methylammonium) perovskite, stoichiometrically prepared as ⟨n⟩ = 5. Within the film, a coexistence of various n-phases is observed instead of solely the n = 5 phase, resulting in an interesting energy landscape for the motion of excitons and charge carriers. We disentangle hot carrier cooling from exciton transfer between low-n and high-n phases using ultrafast time-resolved photoluminescence and transient absorption spectroscopy. Photophysical modeling by target analysis shows that carrier cooling occurring on a subpicosecond time scale is followed by exciton transfer from low-n into high-n phases in ca. 35 ps when the film is excited by 532 or 490 nm light. Carriers in the high-n phase are much longer lived and decay in a ns time window. Overall, our results provide a comprehensive understanding of the photophysics of this material, which helps to optimize quasi-2D MHP materials for a new generation of PV devices.

Concentration dependence on the shape and size of sol-gel-derived yttria-stabilized zirconia ceramic features by soft lithographic patterning.

Typical surface areas of 5 × 5 mm(2) were patterned with high-aspect-ratio micrometer- and submicrometer-sized structures of yttria-stabilized zirconia using a combination of micromolding in capillaries and sol-gel chemistry. The influence of precursor solution concentration and mold geometry on the final shape and dimensions of the patterned structures was investigated. At a precursor concentration of [Zr] = 0.724 mol/dm(3), isolated objects-due to the controlled cracking of patterned films-such as crosses (height 1.4 µm, width 6.0 µm) and "dog bones" (height 800-900 nm, width 900 nm) or patterned films (height 450 nm) were obtained, depending on the mold geometry. Lower precursor concentrations led to differently sized and shaped structures, with changes in dimensions of more than an order of magnitude. Employing a precursor concentration of [Zr] = 0.036 mol/dm(3) yielded isolated rings (height 100-150 nm, line width 20 nm) and squares (height 40 nm, line width 40 nm). A better understanding of the relationship between the precursor concentration, mold geometry, and observed coherent crack patterns in as-dried sol-gel structures may lead to new techniques in patterning isolated features.

Nanoscale patterning of organosilane molecular thin films from the gas phase and its applications: fabrication of multifunctional surfaces and large area molecular templates for site-selective material deposition.

A simple methodology to fabricate micrometer- and nanometer-scale patterned surfaces with multiple chemical functionalities is presented. Patterns with lateral dimensions down to 110 nm were made. The fabrication process involves multistep gas-phase patterning of amine, thiol, alkyl, and fluorinated alkyl-functional organosilane molecules using PDMS molds as shadow masks. Also, a combination process of channel diffused plasma etching of organosilane molecular thin films in combination with masked gas-phase deposition to fabricate multilength scale, multifunctional surfaces is demonstrated.

Influence of the Template Layer on the Structure and Ferroelectric Properties of PbZr0.52Ti0.48O3 Films.

The microstructure of the PbZr0.52Ti0.48O3 (PZT) films is known to influence the ferroelectric properties, but so far mainly the effect of the deposition conditions of the PZT has been investigated. To our knowledge, the influence of the underlying electrode layer and the mechanisms leading to changes in the PZT microstructure have not been explored. Using LaNiO3 (LNO) as the bottom electrode material, we investigated the evolution of the PZT microstructure and ferroelectric properties for changing LNO pulsed-laser deposition conditions. The explored deposition conditions were the O2 pressure, total pressure, and thickness of the electrode layer. Increasing both the O2 pressure and the thickness of the electrode layer changes the growth of PZT from a smooth, dense film to a rough, columnar film. We explain the origin of the change in PZT microstructure as the increased roughness of the electrode layer in relaxing the misfit strain. The strain relaxation mechanism is evidenced by the increase in the crystal phase with bulk LNO unit cell dimensions in comparison to the crystal phase with substrate-clamped unit cell dimensions. We explain the change from a dense to a columnar microstructure as a result of the change in the growth mode from Frank-van der Merwe to Stranski-Krastanov. The ferroelectric properties of the columnar films are improved compared to those of the smooth, dense films. The ability to tune the ferroelectric properties with the microstructure is primarily relevant for ferroelectric applications such as actuators and systems for energy harvesting and storage.

Multilayer films of exfoliated 2D oxide nanosheets by electrospray deposition.

The potential of the electrospray deposition technique as new method to make nanosheet-based multilayer films is evaluated. Densely packed nanosheet-based films with thicknesses of 1-20 nm with rms roughnesses of 2.1-2.4 nm were fabricated on samples of 1 cm2 size with a growth rate of 0.5 nm/min. Electrosprayed Ti0.87O2 nanosheet films were successfully used as oriented growth templates for 40 nm perovskite SrRuO3 thin films grown by pulsed laser deposition. The electrospray method provides a fast and easy alternative to the more commonly used Langmuir-Blodgett (LB) deposition method for nanosheet films.

Patterning functional materials using channel diffused plasma-etched self-assembled monolayer templates.

A simple and cost-effective methodology for large-area micrometer-scale patterning of a wide range of metallic and oxidic functional materials is presented. Self-assembled monolayers (SAM) of alkyl thiols on Au were micropatterned by channel-diffused oxygen plasma etching, a method in which selected areas of SAM were protected from plasma oxidation via a soft lithographic stamp. The patterned SAMs were used as templates for site-selective electrodeposition, electroless deposition and solution-phase deposition of functional materials such as ZnO, Ni, Ag thin films, and ZnO nanowires. The patterned SAMs and functional materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), and tunneling AFM (TUNA).