Planar structures for halide perovskite solar cells have recently garnered attention, due to their simple and low-temperature device fabrication processing. Unfortunately, planar structures typically show I–V  hysteresis and lower stable device efficiency compared with mesoporous structures, especially for TiO2-based n-i-p devices. SnO2, which has a deeper conduction band and higher electron mobility compared with traditional TiO2, could enhance charge transfer from perovskite to electron transport layers, and reduce charge accumulation at the interface. Here we report low-temperature solution-processed SnO2 nanoparticles as an efficient electron transport layer for perovskite solar cells. Our SnO2-based devices are almost free of hysteresis, which we propose is due to the enhancement of electron extraction. By introducing a PbI2 passivation phase in the perovskite layer, we obtain a 19.9 ± 0.6% certified efficiency. The devices can be easily processed under low temperature (150 ∘C), offering an efficient method for the large-scale production of perovskite solar cells. Planar structured perovskite solar cells often show hysteresis and lower efficiency than mesoporous ones. Jiang et al. show that using a SnO2 electron transport layer improves the performance of planar devices, reporting a certified efficiency of 19.9%, and enables a lower processing temperature.

Enhanced electron extraction using SnO 2 for high-efficiency planar-structure HC(NH 2 ) 2 PbI 3 -based perovskite solar cells

The demand for dielectric capacitors with higher energy-storage capability is increasing for power electronic devices due to the rapid development of electronic industry. Existing dielectrics for high-energy-storage capacitors and potential new capacitor technologies are reviewed toward realizing these goals. Various dielectric materials with desirable permittivity and dielectric breakdown strength potentially meeting the device requirements are discussed. However, some significant limitations for current dielectrics can be ascribed to their low permittivity, low breakdown strength, and high hysteresis loss, which will decrease their energy density and efficiency. Thus, the implementation of dielectric materials for high-energy-density applications requires the comprehensive understanding of both the materials design and processing. The optimization of high-energy-storage dielectrics will have far-reaching impacts on the sustainable energy and will be an important research topic in the near future.

Homogeneous/Inhomogeneous-Structured Dielectrics and their Energy-Storage Performances.

The exact role of a defect structure on transition metal compounds for electrocatalytic oxygen evolution reaction (OER), which is a very dynamic process, remains unclear. Studying the structure-activity relationship of defective electrocatalysts under operando conditions is crucial for understanding their intrinsic reaction mechanism and dynamic behavior of defect sites. Co3O4 with rich oxygen vacancy (VO) has been reported to efficiently catalyze OER. Herein, we constructed pure spinel Co3O4 and VO-rich Co3O4 as catalyst models to study the defect mechanism and investigate the dynamic behavior of defect sites during the electrocatalytic OER process by various operando characterizations. Operando electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) implied that the VO could facilitate the pre-oxidation of the low-valence Co (Co2+, part of which was induced by the VO to balance the charge) at a relatively lower applied potential. This observation confirmed that the VO could initialize the surface reconstruction of VO-Co3O4 prior to the occurrence of the OER process. The quasi-operando X-ray photoelectron spectroscopy (XPS) and operando X-ray absorption fine structure (XAFS) results further demonstrated the oxygen vacancies were filled with OH• first for VO-Co3O4 and facilitated pre-oxidation of low-valence Co and promoted reconstruction/deprotonation of intermediate Co-OOH•. This work provides insight into the defect mechanism in Co3O4 for OER in a dynamic way by observing the surface dynamic evolution process of defective electrocatalysts and identifying the real active sites during the electrocatalysis process. The current finding would motivate the community to focus more on the dynamic behavior of defect electrocatalysts.

Operando Identification of the Dynamic Behavior of Oxygen Vacancy-Rich Co3O4 for Oxygen Evolution Reaction.

Light weight and high efficiency are two key factors for microwave absorption materials. In particular, it is extremely important that absorption materials meet the harsh requirements of thermal environments. In this work, multi-wall carbon nanotubes decorated with ZnO nanocrystals (ZnO@MWCNTs) were synthesized by a mild solution-process synthesis. The high-temperature dielectric and microwave absorption properties of SiO2-based composites loaded with ZnO@MWCNTs (ZnO@MWCNTs/SiO2) are investigated in 8.2–12.4 GHz and in the 373–673 K temperature range. The imaginary permittivity e′′ of the composite with 5 wt% loading presents a weak downward trend, while those of the composites with 10 and 15 wt% loading show an upward trend with increasing temperature, which reveals different temperature dependences of e′′. The e′′ for 15 wt% loading is about 10 times that for 5 wt% loading. The maximum loss tangent tan δ values of the composites with 10 and 15 wt% loading exceed 0.8, while that of the composites with 5 wt% loading is less than 0.3. High tan δ is mainly attributed to the conductivity of ZnO@MWCNTs, which is dominated by the hopping of electrons in the ZnO@MWCNT network, which increases with elevated temperature. The addition of ZnO properly adjusts the complex permittivity to endow the ZnO@MWCNT/SiO2 composites with highly efficient and thermally stable microwave absorption coupled with a broad attenuation bandwidth, which almost covers the full X-band for RL ≤ −10 dB. A series of outstanding properties of ZnO@MWCNTs imply that it is a promising functional material in the world of microwave absorption.

Multi-wall carbon nanotubes decorated with ZnO nanocrystals: mild solution-process synthesis and highly efficient microwave absorption properties at elevated temperature

Entropic contributions to the stability of solids are very well understood and the mixing entropy has been used for forming various solids, for instance such as inverse spinels, see Nawrotsky et al., J. Inorg. Nucl. Chem. 29, 2701 (1967) [1]. A particular development was related to high entropy alloys by Yeh et al., Adv. Eng. Mater. 6, 299 (2004) [2] and Cantor et al., Mater. Sci. Eng. A 375–377, 213 (2004) [3] (for recent reviews see Zhang et al., Prog. Mater. Sci. 61, 1 (2014) [4] and Tsai et al., Mater. Res. Lett. 2, 107 (2014) [5]) in which the configurational disorder is responsible for forming simple solid solutions and which are thoroughly studied for various applications especially due to their mechanical properties, e.g. Gludovatz et al., Science 345, 1153 (2014) [6] and Lu et al., Sci. Rep. 4, 6200 (2014) [7], but also electrical properties, Kozelj et al., Phys. Rev. Lett. 113, 107001 (2014) [8], hydrogen storage, Kao et al., Int. J. Hydrogen Energy 35, 9046 (2010) [9], magnetic properties, Zhang et al., Sci. Rep. 3, 1455 (2013) [10]. Many unexplored compositions and properties still remain for this class of materials due to their large phase space. In a recent report it has been shown that the configurational disorder can be used for stabilizing simple solid solutions of oxides, which should normally not form solid solutions, see Rost et al., Nature Commun. 6, 8485 (2015) [11] these new materials were called ”entropy-stabilized oxides”. In this pioneering report, it was shown that mixing five equimolar binary oxides yielded, after heating at high temperature and quenching, an unexpected rock salt structure compound with statistical distribution of the cations in a face centered cubic lattice. Following this seminal study, we show here that these high entropy oxides (named HEOx hereafter) can be substituted by aliovalent elements with a charge compensation mechanism. This possibility largely increases the potential development of new materials by widening their (already complex) phase space. As a first example, we report here that at least one HEOx composition exhibits colossal dielectric constants, which could make it very promising for applications as large-k dielectric materials. (© 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

Colossal dielectric constant in high entropy oxides

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO₂ rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 10(4)) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' In₂(3+)Vo(••)Ti(3+) and 'diamond' shaped Nb₂(5+)Ti(3+)A(Ti) (A = Ti(3+)/In(3+)/Ti(4+)) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO₂. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials

The crystal chemical origin of nanoscale chessboard/diamond ordering in perovskite-related solid solutions of composition Li0.5–3xNd0.5+xTiO3 (LNT, x ∼ 0.02–0.12) is investigated. Experimental and simulated scanning transmission electron microscopy (STEM) images are found to be consistent with the compositional modulation model proposed by previous authors. However, these earlier models do not satisfactorily explain other features observed in high-resolution STEM and TEM images, such as the two-dimensional {100} lattice fringes with the same periodicity, √2ap × √2ap, as the local LNT unit cell viewed along the [001] direction (where ap is the parent perovskite unit cell parameter). Based on bond valence sum calculations, we propose a new set of crystal structures for LNT in which Li ions are primarily bonded to only two O ions, and order one-dimensionally with √2ap periodicity. Bright-field STEM image simulations performed for this new model reproduced the experimentally observed √2ap lattice fringes, thu...

Chessboard/Diamond Nanostructures and the A-site Deficient, Li1/2–3x Nd1/2+xTiO3, Defect Perovskite Solid Solution

Disclosed herein is a material having formula ( A 3+ ((4-5n)/3)-δ B 5+ n)xTi 1-x O 2 , wherein 0<n<0.8,δ and x is such that the material has a rutile structure, 0<n<0.8, δ is between 0 and 0.025 inclusive, A 3+ is a trivalent positive ion and B 5+ is a pentavalent positive ion. A process for making the material, and its use as a dielectric material, are also described.

Giant dielectric constant material

Phase analysis and microwave dielectric properties of BaO–Nd2O3–5TiO2 composite ceramics using variable size TiO2 reagents

Disclosed herein is a material having formula (A 3+ ((4-5n)/3)-δ B 5+ n)xTi 1−x O 2 , wherein 0<n<0.8, δ and x is such that the material has a rutile structure, 0<n<0.8, δ is between 0 and 0.025 inclusive, A 3+ is a trivalent positive ion and B 5− is a pentavalent positive ion. A process for making the material, and its use as a dielectric material, are also described.

Amanda Snashall

Papers

Electron-pinned defect-dipoles for high-performance colossal permittivity materials

Chessboard/Diamond Nanostructures and the A-site Deficient, Li1/2–3x Nd1/2+xTiO3, Defect Perovskite Solid Solution

Giant dielectric constant material

Phase analysis and microwave dielectric properties of BaO–Nd2O3–5TiO2 composite ceramics using variable size TiO2 reagents

High dielectric constant material