Nonhydrogenic exciton spectrum in perovskite CH3NH3PbI3

The excitons in the orthorhombic phase of the perovskite CH₃NH₃PbI₃ are studied using the effective mass approximation. The electron–hole interaction is screened by a distance‐dependent dielectric function, as described by the Haken potential or the Pollmann–Büttner potential. The energy spectrum and the eigenfunctions are calculated for both cases. The results show that the Pollmann–Büttner model, using the corresponding parameters obtained from ab initio calculations, provides better agreement with the experimental results.

     

True nature of active layers in organic solar cells fabricated by sequential casting of donor and acceptor layers

The operation characteristics of nominal bilayer (BL) organic solar cells (OSCs), the active layers (ALs) of which consisted of sequentially casted bottom P3HT donor and top ICBA acceptor layers, resembled those of OSCs with bulk heterojunction (BHJ) ALs. Optical analysis and device simulations showed that such resemblance can be attributed to a similarity in the micromorphology of ALs; as‐deposited BL‐type ALs transformed spontaneously into BHJ‐type ALs. The inclusion of P3HT nanowires (NWs) in the donor layers resulted in different AL micromorphology and consequently a larger power conversion efficiency. Separate assessment of the exciton generation and charge–carrier transport and/or extraction showed that the contribution of P3HT NWs was more prominent in optical effects.

     

Flexible X‐ray detector based on sliced lead iodide crystal

A promising flexible X‐ray detector based on inorganic semiconductor PbI₂ crystal is reported. The sliced crystals mechanically cleaved from an as‐grown PbI₂ crystal act as the absorber directly converting the impinging X‐ray photons to electron hole pairs. Due to the ductile feature of the PbI₂ crystal, the detector can be operated under a highly curved state with the strain on the top surface up to 1.03% and still maintaining effective detection performance. The stable photocurrent and fast response were obtained with the detector repeated bending to a strain of 1.03% for 100 cycles. This work presents an approach for developing efficient and cost‐effective PbI₂‐based flexible X‐ray detector.

     

Nanosphere lithography with variable deposition angle for the production of one‐directional transparent conductors

The production of high quality and cheap transparent electrodes is a fundamental step for a variety of optoelectronic devices. We present a method for the production of transparent conducting films optimised for electrical conduction in one direction. The deposition of a metal film through a perfectly aligned nanosphere‐lithography mask at variable incidence angle gave origin to parallel nanowires with thin interconnections. This structure showed excellent conductivity in one direction and high optical transparency.

Glass substrates under the crystalline areas of the polystyrene‐nanospheres mask.     

Low leakage stoichiometric SrTiO3 dielectric for advanced metal–insulator–metal capacitors

Metal–insulator–metal capacitors (MIMCAP) with stoichiometric SrTiO₃ dielectric were deposited stacking two strontium titanate (STO) layers, followed by intermixing the grain determining Sr‐rich STO seed layer, with the Ti‐rich STO top layer. The resulted stoichiometric SrTiO₃ would have a structure with less defects as demonstrated by internal photoemission experiments. Consequently, the leakage current density is lower compared to Sr‐rich STO which allow further equivalent oxide thickness downscaling.

Schematic of MIMCAP with stoichiometric STO dielectric formed from bottom Sr‐rich STO and top Ti‐rich STO after intermixing during crystallization anneal.     

Ab initio prediction of a new allotrope of two‐dimensional silicon

Silicene, a promising candidate for future electronic devices, has been fabricated only on supporting substrates as silicon atom prefers to form the sp³ hybridization structure. Therefore, it's important to search more stable two‐dimensional (2D) silicon allotropes and several 2D silicon allotropes have been proposed recently. In this work, we predict a new type of 2D silicon allotrope (called OTDS) based on ab initio structure, phonon‐mode and molecular dynamics calculations. OTDS has the in‐plane octagonal tiling (OT) pattern with dumbbell‐like structures and silicon atoms in OTDS are four‐ and three‐coordinated. OTDS is a semiconductor with a large band gap (about 1.5 eV by HSE calculation) and the band gap can be tuned effectively by the in‐plane strain.

Perspective and side views of the atomic structure of OTDS.     

Probing Dy3+ magnetic moments in multiferroic perovskite DyMnO3 by optical spectroscopy

We present a detailed temperature‐dependent (4–300 K) spectroscopic study of DyMnO₃ single crystals with distorted perovskite structure. Energies of 36 crystal‐field levels of Dy³⁺ in paramagnetic DyMnO₃ were determined. The Dy³⁺ ground Kramers doublet does not split at and splits below T_lock = 18 K. The splitting grows fast at temperatures near and reaches Δ₀ ≈ 11 ± 2 cm^–1 at 4 K. Using the experimental temperature dependence Δ₀(T), we calculate the dysprosium magnetic moment m_Dy(T) and the dysprosium contribution into specific heat and magnetic susceptibility. Analysing all the experimental data, we conclude that the Dy–Mn interaction is of the Dzyaloshinskii–Moriya type.

Intensity map in the temperature–wave number coordinates for a spectral line corresponding to the f–f transition of Dy³⁺ in DyMnO₃ and a scheme of the splitting of the Dy ground Kramers doublet. Arrows represent Dy magnetic moments.     

Localization of π‐electron density in twisted bilayer graphene

In bilayer graphene, mutual rotation of layers has strong effect on the electronic structure. We theoretically study the distribution of electron density in twisted bilayer graphene with the rotation angle of 21.8° and find that regions with AA‐like and AB‐like stacking patterns separately contribute to the interlayer low‐energy van Hove singularities. In order to investigate the peculiarities of interlayer coupling, the charge density map between the layers is examined. The presented results reveal localization of π‐electrons between carbon atoms belonging to different graphene layers when they have AA‐like stacking environment, while the interlayer coupling is stronger within AB‐stacked regions.

Charge density map for bilayer graphene with a layer twist of 21.8° (interlayer region).     

Delayed phase separation in growth of organic semiconductor blends with limited intermixing

Binary mixed thin films of picene (C₂₂H₁₄, PIC) and pentacene (C₂₂H₁₄, PEN) consist of crystallites with a statistical occupation of the lattice sites by either PEN or PIC and unit cell parameters continuously changing with the mixing ratio. For high PIC ratios a PIC phase forms which corresponds to a limited intermixing of the two compounds. The growth behavior of these mixtures is investigated in situ and in real‐time using grazing incidence X‐ray diffraction. We observe a delayed phase separation in PIC‐rich blends, i.e. complete intermixing in the monolayer range and the nucleation of a pure PIC‐phase in addition to the intermixed phase starting from the second monolayer.

Growth scenario of picene‐rich pentacene‐picene blends.     

Sulfur impregnation of multi‐walled carbon nanotubes via SF6/NH3 plasma exposure

Plasma treatments are established methods to functionalise carbon nanotubes (CNTs) and modify their surface structure. This paper presents a mild glow‐discharge plasma treatment of aligned arrays of multi‐walled carbon nanotubes employing sulfur hexafluoride (SF₆), ammonia (NH₃), and their mixtures as process gases. For the latter, sulfur was detected at the tip and sidewalls of the nanotubes via energy‐dispersive X‐ray spectroscopy, while electron microscopy served as method to verify the structural integrity of the CNTs after the plasma treatment. This approach provides the basis for an easy and quick alternative to existing sulfur functionalisation methods of MWCNTs. Furthermore, the proposed method can conveniently be applied to carbon nanotube arrays on substrate while preserving their structure and alignment.

SEM‐EDX map of SF₆/NH₃ plasma‐treated multi‐walled carbon nanotubes on substrate. Green, yellow and red correspond to silicon, carbon and sulfur signals, respectively.     

Photocatalytic activity of α‐PbO2‐type TiO2

The α‐PbO₂‐type TiO₂ is synthesized under high‐pressure and high‐temperature environment and it shows higher photocatalytic activity as compared to rutile and anatase under UV irradiation. The reduction in α‐PbO₂‐type TiO₂ induces visible‐light photocatalytic activity. These results indicate that α‐PbO₂‐type TiO₂ is an important candidate material for use in a photocatalytic matrix.

     

Magnetic properties of hard magnetic (Fe,Cr)3Sn2 intermetallic compound

By high‐throughput screening Fe–Sn–Cr, (Fe,Cr)₃Sn₂ (Fe_53.5Cr_6.5Sn₄₀) with high potential as new hard magnetic compound is discovered. To produce the compound in large amounts a special procedure is needed. By quantitative microscopy and magnetometry promising intrinsic properties, J_s ～ 0.9 T, K₁ ～ 1.7 MJ/m³, T_C ～ 612 K, are found with K₁ increasing with temperature.

     

Bulk superconductivity in single‐phase Bi3O2S3

We report the synthesis of single‐phase Bi₃O₂S₃ sample and confirm the occurrence of bulk superconductivity with transition temperature at 5.8 K. The Bi₃O₂S₃ superconductor is categorized as typical type‐II superconductor based on the results of both temperature and magnetic field dependences of magnetization. Hall coefficient measurements give evidence of a multiband character, with a dominant conduction mainly by electron‐like charge carriers. The charge carrier density is about 1.45 × 10¹⁹ cm^–3, suggesting that the system has very low charge carrier density.

     

Electronic structure of formamidinium ions in lead triiodide perovskites

Perovskite formamidinium lead triiodide (FAPbI₃) is a very promising photovoltaic material. Unfortunately, perovskite FAPbI₃ converts to a hexagonal phase at ambient conditions. Herein we study the electronic structure of both perovskite and hexagonal FAPbI₃ films using soft X‐ray absorption near edge structure (XANES) and density functional theory. We find that the C and N 2p states of FA hybridize with the Pb, I states at the conduction band minimum in hexagonal, but not perovskite, FAPbI₃. We also demonstrate that C K‐edge XANES can be used to investigate shifts in the valence band in other organic‐inorganic hybrid perovskites.

Graphical summary of the electronic structure and C K‐edge XANES in both perovskite and hexagonal FAPbI₃ highlighting our findings.     

Investigation of strain‐induced phase transformation in ferroelectric transistor using metal‐nitride gate electrode

In this work, we report a ferroelectric memory with strained‐gate engineering. The memory window of the high strain case was improved by ～71% at the same ferroelectric thickness. The orthorhombic phase transition (from ferroelectric to anti‐ferroelectric transition) plays a key role in realizing negative capacitance effect at high gate electric field. Based on a reliable first principles calculation, we clarify that the gate strain accelerates the phase transformation from metastable monoclinic to orthorhombic and thus largely enhances the ferroelectric polarization without increasing dielectric thickness. This ferroelectric strain technology shows the potential for emerging device application.

     

A high efficiency 3D photovoltaic microwire with carbon nanotubes (CNT)‐quantum dot (QD) hybrid interface

An innovative hybrid QD sensitized photovoltaic carbon nanotubes microyarn has been developed using thermally‐stable and highly conductive carbon nanotubes yarns (CNYs). These CNYs are highly inter‐aligned, ultrastrong and flexible with excellent electrical conductivity, mechanical integrity and catalytic properties. The CNYs are coated with a QD‐incorporated TiO₂ microfilm and intertwined with a second set of CNYs as a counter electrode (CE). The maximum photon to current conversion efficiency (η_AM1.5) achieved with prolonged‐time stability was 5.93%. These cells are capable of efficiently harvesting incident photons regardless of direction and generating photocurrents with high efficiency and operational stability.

     

Photo‐enhanced catalytic activity of spray‐coated Cu2SnSe3 nanoparticle counter electrode for dye‐sensitised solar cells

Cu₂SnSe₃ nanoparticles are synthesised using oleylamine as both a solvent and capping agent and spray coated to form dye‐sensitised solar cell (DSSC) counter electrodes (CEs) using earth‐abundant elements. The film requires annealing at only 400 °C in nitrogen, which is a lower temperature than previous reports of both Cu₂SnSe₃and Cu₂ZnSnSe₄ films, also avoiding the use of Se gas. The composition and phase of the material is confirmed to be kesterite Cu₂SnSe₃. DSSCs using Cu₂SnSe₃ CEs give a power conversion efficiency of 4.87%, compared to 5.35% when using Pt. Electrochemical impedance spectroscopy indicates that the performance of the Cu₂SnSe₃ CE is enhanced under illumination, leading to a drop in the charge transfer resistance. This illumination‐induced enhancement of the catalytic activity provides a novel mechanism for the enhancement of CE performance in DSSCs.

     

Microstructural identification of Cu in solar cells sensitive to light‐induced degradation

Light‐induced degradation (mc‐LID or LeTID) can lead to a severe efficiency loss in multi‐crystalline solar cells. The underlying mechanism clearly distinguishes from known mechanisms as B‐O‐LID and Fe‐B‐LID. Various defect models have been suggested for mc‐LID mainly based on metal impurities, including Cu which is known to cause light‐induced degradation. We investigate mc‐LID sensitive PERC cells that show an efficiency degradation of 15%_rel. The weaker degradation of the grain boundaries (GBs) typical for mc‐LID is identified and further investigated from front and rear side with respect to recombination activities. The combination of local electrical measurements (LBIC), target preparation (REM, FIB) and element analysis (EDX, TEM) unveil Cu‐containing precipitates at the rear side of the solar cells. They accumulate at grain boundaries and at the rear surface of the Si‐bulk material where the passivation stack is damaged. We conclude that Cu originates from the cell material and discuss its relation to mc‐LID.

LBIC mapping (EQE at fixed wavelength) of a degraded mc‐Si PERC cell from front and rear side results in qualitatively different appearance of GBs.