Structural characterization and electronic properties of Ni/rubrene bilayers with alternative stacking sequences.

Recent progress in organic electronics has attracted interest due to their excellent characteristics that include photovoltaic, light emission, and semiconducting behaviours. Spin-induced properties play important roles in organic electronics, while introducing spin into an organic layer in which spin responses, such as a weak spin-orbital coupling and long spin-relaxation time, allows a variety of spintronic applications to be achieved. However, such spin responses are rapidly attenuated by misalignment in the electronic structure of hybrid structures. We report herein on the energy level diagrams of Ni/rubrene bilayers that can be tuned by an alternating stacking. The band edges of the highest occupied molecular orbital (HOMO) levels were determined to be 1.24 and 0.48 eV relative to the Fermi level for Ni/rubrene/Si and rubrene/Ni/Si bilayers, respectively. This raises a possibility of accumulating electric dipoles at the ferromagnetic/organic semiconductor (FM/OSC) interface, which would inhibit the transfer of spin in the OSC layer. This phenomenon is caused by the formation of a Schottky-like barrier in the rubrene/Ni heterostructures. According to the information about the band edges of the HOMO levels, schematic plots of the HOMO shift in the electronic structure of the bilayers are presented. Based on the lower value of the effective uniaxial anisotropy for Ni/rubrene/Si, the uniaxial anisotropy was suppressed compared to that of rubrene/Ni/Si. The characteristics of the formation of Schottky barriers at the FM/OSC interface have an impact on the temperature-dependent spin states in the bilayers.

Impact of a rubrene buffer layer on the dynamic magnetic behavior of nickel layers on Si(100).

Interfaces of ferromagnetic/organic material hybrid structures refer to the spin interface that governs physical properties for achieving high spin polarization, low impedance mismatch, and long spin relaxation. Spintronics can add new functionalities to electronic devices by taking advantage of the spin degree of freedom of electrons, which makes understanding the dynamic magnetic properties of magnetic films important for spintronic device applications. Our knowledge regarding the magnetic dynamics and magnetic anisotropy of combining ferromagnetic layer and organic semiconductor by microwave-dependent magnetic measurements remains limited. Herein, we report the impact of an organic layer on the dynamic magnetic behavior of nickel/rubrene bilayers deposited on a Si(100) substrate. From magnetic dynamic measurements, opposite signs of effective magnetic fields between the in-plane (IP) and out-of-plane (OP) configurations suggest that the magnetization of Ni(x)/rubrene/Si prefers to coexist. A shift in OP resonance fields to higher values can mainly be attributed to the enhanced second-order anisotropy parameter K2 value. Based on IP measurements, a two-magnon scattering mechanism is dominant for thin Ni(x)/rubrene/Si bilayers. By adding a rubrene layer, the highly stable IP combined with the tunable OP ferromagnetic resonance spectra for Ni(x)/rubrene/Si bilayers make them promising materials for use in microwave magnetic devices and spintronics with controllable perpendicular magnetic anisotropy.

Self-assembled magnetic heterostructure of Co/DLC films.

In order to adapt to the quick and large amount of necessity in data flow for 5G cloud generation, it is necessary to develop a technology of warm storage device in market which takes a great balance between the reading/writing performance and the price per storage capacity. The technologies of warm storage devices are assumed to adopt phase change memory (PCM), resistive random access memory or magnetoresistive random access memory which have the highest possibilities to 5G structures and magnetic properties of Co on non-hydrogenated diamond like carbon (DLC)/Si(100) films and Co/DLC interface are investigated. The self-assembled magnetic heterostructure is firstly reported in hexagonal close packing Co layers perpendicular magnetic anisotropy (PMA) on Co carbide layers (in-plane) during Co deposited on DLC/Si(100). A PMA/in-plane magnetic heterostructure is expected to have the highest switching current to the energy barrier ratio of near 4 in previous report, which has great potential for developing warm memory devices. Based on these unique characteristics, we provide a novel design called magnetic anisotropy-phase change memory (Mani-PCM) which can impact the developing blueprint of memory. The working process of Mani-PCM includes in set, reset and read states as a universal PCM. This brand new technology is highly promising as warm memory devices including high reading/writing performance and economical price per storage capacity.

Comparisons of magnetic defects and coercive forces for Co/Si(100) and Co/rubrene/Si(100).

Spintronics can add new functionalities to electronic devices by utilizing the spin degree of freedom of electrons. Investigating magnetic defects is crucial for the performance of spintronics devices. However, the effects of magnetic defects that are introduced by the presence of organic materials on their magnetic properties remain unclear. Herein, we report on a novel method using rubrene combined with Kerr microscopy that enables quantitative and direct measurements of magnetic defect density. For Co/Si(100) at a magnetic field near the coercivity value, Kerr microscopy images show a dark image with some magnetic defects. Because of domain wall motion, small patches gradually change the contrast. These magnetic defects are immovable at different magnetic fields and serve as pinning sites for domain wall motion. Experimental evidence shows that coercive force can be reduced by controlling the magnetic defect density by introducing small amounts of rubrene into the films. Furthermore, direct quantitative measurements of magnetic defects show both a one-dimensional bowing of domain walls and strong defect-domain wall interactions in the films. Based on these findings, we propose a viable strategy for reducing the coercive force of Co/Si(100) by controlling the magnetic defect density and this new information promises to be valuable for future applications of spintronics devices.

Variations of the elastic modulus perpendicular to the surface of rubrene bilayer films.

Investigations exploring the inherent mechanical properties of electronic materials have grown rapidly in recent years largely because they are important in developing flexible electronics, organic displays and sensors. However, our understanding of the mechanical properties of organic semiconductors with a thin-film form remains limited. We report herein on an investigation of the structures and related elastic moduli perpendicular to the surface of a rubrene thin film. A rubrene/Si(100) film typically has a cluster-type morphology mainly comprising crystalline nanodomains within the film. We propose a structural bilayer model that can be used to explain the layered nature or characteristics of the rubrene films. As the film thickness is increased, the enhancement in elastic modulus can be attributed to the presence of a soft surface layer on a hard underlayer. Based on four-point probe measurements, the bilayered nature of such materials can be used to characterize their electrical resistive behavior while interfacial roughness is sensitive to the transport paths of conduction electrons. This information is valuable for future applications of organic semiconductors in flexible devices.

Enhancing the magnetic anisotropy energy by tuning the contact areas of Ag and Ni at the Ag/Ni interface.

Modifying the interfacial conditions of magnetic layers by capping with overlayers can efficiently enhance the magnetic functionality of a material. However, the mechanisms responsible for this are closely related to the crystalline structure, compositional combinations, and interfacial quality, and are generally complex. In this contribution, we explored the use of Ag ultrathin overlayers on annealed . A method for preparing magnetic layers with different levels of enhanced magnetic anisotropy energy was developed. The method essentially involves simply modifying the contact area of the metallic/magnetic interface. A rougher interface results in a larger contact area between the Ag and Ni layers, resulting in an increase in magnetic anisotropy energy. Moreover, post-annealing treatments led to the segregation of Ni atoms, thus making the enhancement in the coercive force even more efficient. A model permits an understanding of the contact area and a strategy for enhancing the magnetic anisotropy energy and the coercive force was developed. Our approaches and the developed model promise to be helpful in terms of developing potential applications of ultrathin magnetic layers in the area of spintronics.

Spin reorientation transitions and structures of electrodeposited Ni/Cu(100) ultrathin films with and without Pb additives.

Magnetic properties and surface structures of Ni/Cu(100) ultrathin films are studied by means of magneto-optical Kerr effect and in situ scanning tunneling microscopy in combination with cyclic voltammetry. At the initial stage of Ni deposition on a Cu(100) electrode, nickel atoms attach onto the steps and the surface shows single atomic steps corresponding to a layer-by-layer growth. For thicker Ni/Cu(100) films, nanometer-size clusters are randomly distributed on the surface showing a three-dimensional island growth. For thinner Ni layers in the coherent region, the magnetic anisotropy energy of the Cl-electrolyte/Ni interface is small. The reduction of squareness of the hysteresis loops is related to the inhomogeneous growth of the Ni layers. For thicker Ni layers in the incoherent region, the negative value of interface anisotropy for the Cl-electrolyte/Ni interface has a strong impact on perpendicular magnetic anisotropy and plays an important role on the reduction of the Ni thickness for spin reorientation transition in the electrolyte condition. By adding Pb additives, the deposition of a Pb wetting layer causes a defaceting phenomenon and the hydrogen evolution reaction is reduced. As the Ni thickness increases, the growth of Ni changes from layer-by-layer to quasi-two-dimensional islands with a flat top layer. With a Pb additive, the spin reorientation transitions of the Ni/Cu(100) system are not significantly influenced. However, due to the change of the growth mode by Pb atoms as a surfactant, the squareness of the hysteresis loops is enhanced for all the Ni thicknesses.

Dramatic improvement in the stability and mechanism of high-performance inverted polymer solar cells featuring a solution-processed buffer layer.

In this study, we demonstrate inverted PTB7:PC71BM polymer solar cells (PSCs) featuring a solution-processed s-MoO3 hole transport layer (HTL) that can, after thermal aging at 85 °C, retain their initial power conversion efficiency (PCE) for at least 2200 h. The T80 lifetimes of the PSCs incorporating the novel s-MoO3 HTL were up to ten times greater than those currently reported for PTB7- or low-band-gap polymer:PCBM PSCs, the result of the inhibition of burn-in losses and long-term degradation under various heat-equivalent testing conditions. We used X-ray photoelectron spectroscopy (XPS) to study devices containing thermally deposited t-MoO3 and s-MoO3 HTLs and obtain a mechanistic understanding of how the robust HTL is formed and how it prevented the PSCs from undergoing thermal degradation. Heat tests revealed that the mechanisms of thermal inter-diffusion and interaction of various elements within active layer/HTL/Ag electrodes controlled by the s-MoO3 HTL were dramatically different from those controlled by the t-MoO3 HTL. The new prevention mechanism revealed here can provide the conceptual strategy for designing the buffer layer in the future. The PCEs of PSCs featuring s-MoO3 HTLs, measured in damp-heat (65 °C/65% RH; 85 °C per air) and light soaking tests, confirmed their excellent stability. Such solution-processed MoO3 HTLs appear to have great potential as replacements for commonly used t-MoO3 HTLs.

Strain driven phase transition and mechanism for Fe/Ir(111) films.

By way of introducing heterogeneous interfaces, the stabilization of crystallographic phases is critical to a viable strategy for developing materials with novel characteristics, such as occurrence of new structure phase, anomalous enhancement in magnetic moment, enhancement of efficiency as nanoportals. Because of the different lattice structures at the interface, heterogeneous interfaces serve as a platform for controlling pseudomorphic growth, nanostructure evolution and formation of strained clusters. However, our knowledge related to the strain accumulation phenomenon in ultrathin Fe layers on face-centered cubic (fcc) substrates remains limited. For Fe deposited on Ir(111), here we found the existence of strain accumulation at the interface and demonstrate a strain driven phase transition in which fcc-Fe is transformed to a bcc phase. By substituting the bulk modulus and the shear modulus and the experimental results of lattice parameters in cubic geometry, we obtain the strain energy density for different Fe thicknesses. A limited distortion mechanism is proposed for correlating the increasing interfacial strain energy, the surface energy, and a critical thickness. The calculation shows that the strained layers undergo a phase transition to the bulk structure above the critical thickness. The results are well consistent with experimental measurements. The strain driven phase transition and mechanism presented herein provide a fundamental understanding of strain accumulation at the bcc/fcc interface.

Molecular structures of dicarboxylated viologens on a Cu(100) surface during an ongoing charge transfer reaction.

Molecular structures of dicarboxylated viologens (1,1'-bis (7-carboxyheptyl)-4,4'-bipyridinium dibromide molecules, V-(C(7)-COOH)(2)) on a Cu(100) surface are studied by means of in situ scanning tunneling microscopy (STM) in combination with cyclic voltammetry (CV). Self-assembled monolayers of adsorbed dicarboxylated viologens form during an ongoing charge transfer reaction. Mainly six structures of the organic molecules are observed, including a dot array, metastable phases, stripe patterns, a closed stacking stripe pattern, chloride desorption, and a dimer phase. The molecular structural models for all the structures have been successfully established. The carboxylated viologen molecules in the dicationic state prefer the face-on configuration on the surface and form the dot array phase. The other phases are shown by the radical state of the viologens. The metastable phases show two forms: cluster-like and stripe pattern-like structures. Main features of the metastable phases are face-to-face configurations of the radical viologens in π-stacking form between neighboring parallel bipyridiniums. Hydrogen bonding is considered to be the major factor in constructing the network of the stripe pattern. At a more negative potential, the bilayers of the stripe pattern transform to be a monolayer of the closed stacking stripe pattern because of the enhanced electrostatic force. The closed stacking stripe pattern is stable on the surface until chloride desorption. As the chloride anions desorb from the Cu(100) surface, the disordered dimers transform to an ordered dimer phase on a Cu(100)-1×1 surface due to the hydrogen bonding between neighboring dimer rows.

A practical method for fabricating superparamagnetic films and the mechanism involved.

Due to the widespread applications of biosensors, such as in magnetic resonance imaging, cancer detection and drug delivery, the use of superparamagnetic materials for preparing biosensors has increased greatly. We report herein on a strategy toward fabrication of a nanoscale biosensor composed of superparamagnetic films. On increasing the film thickness of magnetic layers, a phase transition typically occurs from either a low-Curie-temperature state or a superparamagnetic state to a ferromagnetic state. A new finding is demonstrated wherein a phase transition of such a superparamagnetic phase can be induced by controlling the thickness of ultrathin ferromagnetic layers with perpendicular magnetic anisotropy. Both the M-H curve with zero coercive force at 300 K and deviations of the normalized hysteresis loop at 2 K confirm the superparamagnetic state of Co/Ir(111) at room temperature. An overstrained film transforming into clusters (OFTC) model based on the new finding and our experimental evidence is proposed for modeling this phenomenon. From the energetic point of view of the OFTC model, we propose a limited distortion mechanism that can be useful in determining the critical thickness for the phase transition. This mechanism considers the balance between interfacial strain energy and surface free energy. A method for producing superparamagnetic films by taking advantage of the accumulation of strain and relaxation is reported.

Enhancing silicide formation in Ni/Si(111) by Ag-Si particles at the interface.

Compound formation at a metal/semiconductor interface plays crucial roles in the properties of many material systems. Applications of Ni silicides span numerous areas and have the potential to be used as new functionalities. However, the magnetic properties of ultrathin Ni layers on silicon surfaces and related chemical compositions at the interface are not fully understood and the influence of Ag additives on the reactivity of Ni/Si(111) remain unclear. We report herein on the fact that the dominant species produced at the interface is NiSi, which is produced by the spontaneous formation of strong bonds between Ni and Si atoms. Assuming that a Ni layer is formed over a NiSi layer with the total coverage as a constraint, we established a chemical shift-related concentration model that, in effect, represents a practical method for determining the amount of ultrathin Ni silicides that are produced at the buried interface. The formation of Ag-Si particles provide a viable strategy for enhancing silicide formation via a specific interaction transfer mechanism, even at room temperature. The mechanism is related to differences in the enthalpies of formation ΔHAg-Si, ΔHNi-Ag, and ΔHNi-Si, for these phases and provides insights into strategies for producing ultrathin silicides at a buried interface.

Tuning coercive force by adjusting electric potential in solution processed Co/Pt(111) and the mechanism involved.

A combination of a solution process and the control of the electric potential for magnetism represents a new approach to operating spintronic devices with a highly controlled efficiency and lower power consumption with reduced production cost. As a paradigmatic example, we investigated Co/Pt(111) in the Bloch-wall regime. The depression in coercive force was detected by applying a negative electric potential in an electrolytic solution. The reversible control of coercive force by varying the electric potential within few hundred millivolts is demonstrated. By changing the electric potential in ferromagnetic layers with smaller thicknesses, the efficiency for controlling the tunable coercive force becomes higher. Assuming that the pinning domains are independent of the applied electric potential, an electric potential tuning-magnetic anisotropy energy model was derived and provided insights into our knowledge of the relation between the electric potential tuning coercive force and the thickness of the ferromagnetic layer. Based on the fact that the coercive force can be tuned by changing the electric potential using a solution process, we developed a novel concept of electric-potential-tuned magnetic recording, resulting in a stable recording media with a high degree of writing ability.

Magnetic domain imaging of nano-magnetic films using magnetic force microscopy with polar and longitudinally magnetized tips.

Perpendicular or parallel magnetic fields are used to magnetize the tips used in magnetic force microscopy (MFM). In this process, perpendicular or parallel magnetic dipole moments are produced on the tip plane, thus leading to the formation of polar magnetized tips (PM-tips) or longitudinally magnetized tips (LM-tips), respectively. The resolution of an MFM image of a magneto-optic disk is used for calibration of these tips, and the saturated magnetic fields of the PM- and LM-tips are found to be 2720 Oe and 680 Oe, respectively. Because both tips can simultaneously magnetize the sample during the scanning process when measuring a Co thin film, clear MFM images are captured, which enable the identification of magnetizable regions and the distribution of the magnetic domains on the sample surface. These results will be useful for improving the manufacturing processes required for soft nano-magnetic film production.