Solution Atomic Layer Deposition of Smooth, Continuous, Crystalline Metal-Organic Framework Thin Films.

For the first time, a procedure has been established for the growth of surface-anchored metal-organic framework (SURMOF) copper(II) benzene-1,4-dicarboxylate (Cu-BDC) thin films of thickness control with single molecule accuracy. For this, we exploit the novel method solution atomic layer deposition (sALD). The sALD growth rate has been determined at 4.5 Å per cycle. The compact and dense SURMOF films grown at room temperature by sALD possess a vastly superior film thickness uniformity than those deposited by conventional solution-based techniques, such as dipping and spraying while featuring clear crystallinity from 100 nm thickness. The highly controlled layer-by-layer growth mechanism of sALD proves crucial to prevent unwanted side reactions such as Ostwald ripening or detrimental island growth, ensuring continuous Cu-BDC film coverage. This successful demonstration of sALD-grown compact continuous Cu-BDC SURMOF films is a paradigm change and provides a key advancement enabling a multitude of applications that require continuous and ultrathin coatings while maintaining tight film thickness specifications, which were previously unattainable with conventional solution-based growth methods.

A Geometrically Well-Defined and Systematically Tunable Experimental Model to Transition from Planar to Mesoporous Perovskite Solar Cells.

A series of perovskite solar cells with systematically varying surface area of the interface between n-type electron conducting layer (TiO2) and perovskite are prepared by using an ordered array of straight, cylindrical nanopores generated by anodizing an aluminum layer evaporated onto a transparent conducting electrode. A series of samples with pore length varied from 100 to 500 nm are compared to each other and complemented by a classical planar cell and a mesoporous counterpart. All samples are characterized in terms of morphology, chemistry, optical properties, and performance. All samples absorb light to the same degree, and the increased interface area does not generate enhanced recombination. However, the short circuit current density increases monotonically with the specific surface area, indicating improved charge extraction efficiency. The importance of the slow interfacial rearrangement of ions associated with planar perovskite cells is shown to decrease in a systematic manner as the interfacial surface area increases. The results demonstrate that planar and mesoporous cells obey to the same physical principles and differ from each other quantitatively, not qualitatively. Additionally, the study shows that a significantly lower TiO2 surface area compared to mesoporous TiO2 is needed for an equal charge extraction.

Stabilizing an ultrathin MoS2 layer during electrocatalytic hydrogen evolution with a crystalline SnO2 underlayer.

Amorphous MoS2 has been investigated abundantly as a catalyst for hydrogen evolution. Not only its performance but also its chemical stability in acidic conditions have been reported widely. However, its adhesion has not been studied systematically in the electrochemical context. The use of MoS2 as a lubricant is not auspicious for this purpose. In this work, we start with a macroporous anodic alumina template as a model support, add an underlayer of SnO2 to provide electrical conduction and adhesion, then provide the catalytically active, amorphous MoS2 material by atomic layer deposition (ALD). The composition, morphology, and crystalline or amorphous character of all layers are confirmed by spectroscopic ellipsometry, X-ray photoelectron spectroscopy, grazing incidence X-ray diffractometry, scanning electron microscopy and energy dispersive X-ray spectroscopy. The electrocatalytic water reduction performance of the macroporous AAO/SnO2/MoS2 electrodes, quantified by voltammetry, steady-state chronoamperometry and electrochemical impedance spectroscopy, is improved by annealing the SnO2 layer prior to MoS2 deposition. Varying the geometric parameters of the electrode composite yields an optimized performance of 10 mA cm-2 at 0.22 V overpotential, with a catalyst loading of 0.16 mg cm-2. The electrode's stability is contingent on SnO2 crystallinity. Amorphous SnO2 allows for a gradual dewetting of the originally continuous MoS2 layer over wide areas. In stark contrast to this, crystalline SnO2 maintains the continuity of MoS2 until at least 0.3 V overpotential.

Solid state interdigitated Sb2S3 based TiO2 nanotube solar cells.

TiO2 nanotubes generated by anodization of metallic titanium sputter-coated on indium tin oxide (ITO) substrates are used as a conductive scaffold for all solid-state Sb2S3-sensitized extremely thin absorber (ETA) solar cells. A blocking layer of TiO2 placed between Ti and ITO in combination with optimized Ti deposition and anodization conditions enables the formation of crack-free layers of straight, cylindrical TiO2 nanotubes of tunable length and diameter. ALD (atomic layer deposition) is subsequently used to coat this substrate conformally with a highly pure Sb2S3 light absorber layer under an inert atmosphere. The high absorption coefficient of Sb2S3 as compared to molecular dyes allows for the utilization of very short nanotubes, which facilitates the infiltration of the organic hole transport material and formation of a p-i-n heterojunction in an interdigitated and tunable geometry. We investigate the influence of nanotube length and of the absorber thickness to enhance the photocurrent value to twice that of planar reference structures.

Synthesis, Characterization, and Properties of Iron(II) Spin-Crossover Molecular Photoswitches Functioning at Room Temperature.

Spin-crossover molecular switches [FeII(H2B(pz)2)2L] (L = novel phenanthroline-based ligands featuring photochromic diarylethene units; pz = 1-pyrazolyl) were synthesized and thoroughly characterized by variable-temperature X-ray crystallography, Mössbauer spectroscopy, and magnetic measurements. The effect of substituents introduced into the phenanthroline backbone (L2) and into the photochromic diarylethene unit (L3) on photophysical properties of metal-free ligands and spin-crossover iron(II) complexes 2 and 3, respectively, were investigated in detail. Both ligands and complexes could be switched with light in solution at room temperature. The photocyclization of 2 was accompanied by a high-spin to low-spin photoconversion determined at 19%. The closed-ring isomers of L3 and 3 reveal the lifetimes in the range of minutes, whereas those of L2 and 2 are thermally stable for days in solutions at room temperature. The reversibility of the photoswitching can be improved by avoiding the photostationary states. Prospective introduction of anchoring groups to the phenanthroline backbone might allow the construction of chemisorbed self-assembled monolayers of spin-crossover species switchable with light at room temperature.

Design Rules for Oxygen Evolution Catalysis at Porous Iron Oxide Electrodes: A 1000-Fold Current Density Increase.

Nanotubular iron(III) oxide electrodes are optimized for catalytic efficiency in the water oxidation reaction at neutral pH. The nanostructured electrodes are prepared from anodic alumina templates, which are coated with Fe2 O3 by atomic layer deposition. Scanning helium ion microscopy, X-ray diffraction, and Raman spectroscopy are used to characterize the morphologies and phases of samples submitted to various treatments. These methods demonstrate the contrasting effects of thermal annealing and electrochemical treatment. The electrochemical performances of the corresponding electrodes under dark conditions are quantified by steady-state electrolysis and electrochemical impedance spectroscopy. A rough and amorphous Fe2 O3 with phosphate incorporation is critical for the optimization of the water oxidation reaction. For the ideal pore length of 17 µm, the maximum catalytic turnover is reached with an effective current density of 140 µA cm-2 at an applied overpotential of 0.49 V.

Photochemical Energy Storage and Electrochemically Triggered Energy Release in the Norbornadiene-Quadricyclane System: UV Photochemistry and IR Spectroelectrochemistry in a Combined Experiment.

The two valence isomers norbornadiene (NBD) and quadricyclane (QC) enable solar energy storage in a single molecule system. We present a new photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) experiment, which allows monitoring of the complete energy storage and release cycle by in situ vibrational spectroscopy. Both processes were investigated, the photochemical conversion from NBD to QC using the photosensitizer 4,4'-bis(dimethylamino)benzophenone (Michler's ketone, MK) and the electrochemically triggered cycloreversion from QC to NBD. Photochemical conversion was obtained with characteristic conversion times on the order of 500 ms. All experiments were performed under full potential control in a thin-layer configuration with a Pt(111) working electrode. The vibrational spectra of NBD, QC, and MK were analyzed in the fingerprint region, permitting quantitative analysis of the spectroscopic data. We determined selectivities for both the photochemical conversion and the electrochemical cycloreversion and identified the critical steps that limit the reversibility of the storage cycle.

Energy Storage in Strained Organic Molecules: (Spectro)Electrochemical Characterization of Norbornadiene and Quadricyclane.

We have investigated the electrochemically triggered cycloreversion of quadricyclane (QC) to norbornadiene (NBD), a system that holds the potential to combine both energy storage and conversion in a single molecule. Unambiguous voltammetric traces are obtained for pure NBD and pure QC, the latter a strained polycyclic isomer of the former. The difference in redox potentials is smaller than the energy difference between the neutral molecules. This is owing to a significant energy difference between the corresponding radical cations, as demonstrated by density functional theory (DFT) calculations. The vibrational modes of each pure compound are characterized experimentally in the fingerprint region and identified by DFT methods. Thermal and electrochemical transformations of NBD and QC are monitored in situ by IR spectroelectrochemical methods. The kinetics of the cycloreversion of QC to NBD, which is catalyzed by oxidizing equivalents, can be controlled by an applied electrode potential, which implies the ability to adjust in real time the release of thermal power stored in QC.

A large electrochemical setup for the anodization of aluminum towards highly ordered arrays of cylindrical nanopores.

A new electrochemical setup and the associated procedures for growing ordered anodic aluminum oxide pore arrays on large surfaces are presented. The typical size of the samples is 14 × 14 cm(2). The most crucial experimental parameters that allow for the stabilization of the high-field procedures are a very efficient cooling of sample and electrolyte, as well as the initial ramping up of the voltage at an accurately defined rate. The morphology of the cylindrical, parallel alumina pores is similar to those obtained on smaller scales with standard setups. Our setup facilitates the availability of porous anodic alumina as a template system for a number of applications.