Protective Capping Layer Research Articles

Scalable Fabrication of Black Phosphorous Films for Infrared Photodetector Arrays.

Bulk black phosphorous (bP) exhibits excellent infrared (IR) optoelectronic properties, but most reported bP IR photodetectors are fabricated from single exfoliated flakes with lateral sizes of <100µm. Here, scalable thin films of bP suitable for IR photodetector arrays are realized through a tailored solution-deposition method. The properties of the bP film and their protective capping layers are optimized to fabricate bP IR photoconductors exhibiting specific detectivities up to 4.0×108cm Hz1/2 W-1 with fast 30/60 µs rise/fall times under λ = 2.2µm illumination. The scalability of the bP thin film fabrication is demonstrated by fabricating a linear array of 25 bP photodetectors and obtaining 25×25pixel IR images at ≈203ppi with good spatial fidelity. This research demonstrates a commercially viable method of fabricating scalable bP thin films for optoelectronic devices including room temperature-operable IR photodetector arrays.

Stress-Relieving Carboxylated Polythiophene/Single-Walled Carbon Nanotube Conductive Layer for Stable Silicon Microparticle Anodes in Lithium-Ion Batteries.

Stress-relieving and electrically conductive single-walled carbon nanotubes (SWNTs) and conjugated polymer, poly[3-(potassium-4-butanoate)thiophene] (PPBT), wrapped silicon microparticles (Si MPs) have been developed as a composite active material to overcome technical challenges such as intrinsically low electrical conductivity, low initial Coulombic efficiency, and stress-induced fracture due to severe volume changes of Si-based anodes for lithium-ion batteries (LIBs). The PPBT/SWNT protective layer surrounding the surface of the microparticles physically limits volume changes and inhibits continuous solid electrolyte interphase (SEI) layer formation that leads to severe pulverization and capacity loss during cycling, thereby maintaining electrode integrity. PPBT/SWNT-coated Si MP anodes exhibited high initial Coulombic efficiency (85%) and stable capacity retention (0.027% decay per cycle) with a reversible capacity of 1894 mA h g-1 after 300 cycles at a current density of 2 A g-1, 3.3 times higher than pristine Si MP anodes. The stress relaxation and underlying mechanism associated with the incorporation of the PPBT/SWNT layer were interpreted by quasi-deterministic and quantitative stress analyses of SWNTs through in situ Raman spectroscopy. PPBT/SWNT@Si MP anodes can maintain reversible stress recovery and 45% less variation in tensile stress compared with SWNT@Si MP anodes during cycling. The results verify the benefits of stress relaxation via a protective capping layer and present an efficient strategy to achieve long cycle life for Si-based anodes for next-generation LIBs.

Performance enhancement in spin transfer torque magnetic random access memory through in situ cap layer optimization

Magnetic tunnel junctions (MTJs), a key component of spin transfer torque magnetic random access memory, are typically fabricated using two main processes: plasma etching and in situ protective cap layer deposition. It has been found that while the etching process predominantly affects MTJ performance, the cap layer process can further enhance electrical and magnetic properties. In this study, we achieved performance improvements in MTJs by optimizing the cap layer deposition process through various experimental methods, such as modifying the gas mixtures used in the deposition process and incorporating a novel post-plasma treatment. During the deposition of the silicon nitride (SiNx) cap layer, N-rich dissociated compounds can induce passivation of the MTJ layer, leading to additional loss of tunneling magnetoresistance (TMR) and coercive field (Hc). To circumvent this challenge, we prioritized modifying the gas ratio in the SiNx deposition process. Additionally, hydrogen introduced during SiNx deposition can penetrate the MTJ pillars and degrade their properties. To mitigate this, we developed a novel post-nitrogen plasma treatment in a plasma-enhanced chemical vapor deposition chamber, which effectively desorbed the excess hydrogen from the MTJ film stack. As a result of these optimized processes, the TMR loss, compared to a blanket wafer, was reduced from 25% to 8%, and Hc increased by up to 33% for the same stack, achieving significant performance enhancements.

Structural and opto-electronic engineering with ZnS ETL via PVD technique for efficient and durable heterojunction perovskite solar cells

This study presents a comprehensive investigation into fabrication and characterization of HJPSC leveraging chalcogenide Zinc Sulphide (ZnS) thin films as ETL and Selenium (Se) as a protective capping layer through PVD technique. ZnS thin films annealed at 200 °C, 300 °C and 400 °C were systematically analyzed for their structural and opto-electronic properties. Among them, ZnS-1, annealed at 200 °C, demonstrated superior performance with high transmittance, optimal crystallite size, wide bandgap, lowest photoluminescence intensity, high conductivity and low resistivity. Consequently, ZnS-1 was selected as the ETL for HJPSC fabrication. The HJPSC device was fabricated with ZnS/MAPbI3--Se/Ag as device structure with Se as capping layer. SEM images confirmed the smooth and continuous nature of the ZnS-1 film, while X-Ray diffraction analysis validated the purity and crystallinity of MAPbI3 perovskite layer. The successful alignment of the perovskite absorption band with the solar cell emission spectrum obtained by UV–Vis spectra highlighted the potential for efficient solar energy conversion. J-V characteristics of the HJPSC device exhibited a high short-circuit current (Jsc) of 20.18 mA/cm2, an open-circuit voltage (Voc) of 0.99 V, a power conversion efficiency (PCE) of 9.1 % and fill factor (FF) of 45.7 % was accredited to improved electron conductance and of ZnS-1 as an ETL.

Is Ba3In2O6 a high-Tc superconductor?

It has been suggested that Ba3In2O6 might be a high-Tc superconductor. Experimental investigation of the properties of Ba3In2O6 was long inhibited by its instability in air. Recently epitaxial Ba3In2O6 with a protective capping layer was demonstrated, which finally allows its electronic characterization. The optical bandgap of Ba3In2O6 is determined to be 2.99 eV in-the (001) plane and 2.83 eV along the c-axis direction by spectroscopic ellipsometry. First-principles calculations were carried out, yielding a result in good agreement with the experimental value. Various dopants were explored to induce (super-)conductivity in this otherwise insulating material. Neither A- nor B-site doping proved successful. The underlying reason is predominately the formation of oxygen interstitials as revealed by scanning transmission electron microscopy and first-principles calculations. Additional efforts to induce superconductivity were investigated, including surface alkali doping, optical pumping, and hydrogen reduction. To probe liquid-ion gating, Ba3In2O6 was successfully grown epitaxially on an epitaxial SrRuO3 bottom electrode. So far none of these efforts induced superconductivity in Ba3In2O6, leaving the answer to the initial question of whether Ba3In2O6 is a high-Tc superconductor to be ‘no’ thus far.

Framework for Engineering of Spin Defects in Hexagonal Boron Nitride by Focused Ion Beams

AbstractHexagonal boron nitride (hBN) is gaining interest as a wide bandgap van der Waals host of optically active spin defects for quantum technologies. Most studies of the spin‐photon interface in hBN focus on the negatively charged boron vacancy (VB−) defect, which is typically fabricated by ion irradiation. However, the applicability and wide deployment of VB− defects is limited by VB− fabrication methods which lack robustness and reproducibility, particularly when applied to thin flakes (≲10 nm) of hBN. Here, two key factors are elucidated that underpin the formation and quenching of VB− centers by ion irradiation—density of defects generated in the hBN lattice and recoil‐implantation of foreign atoms into hBN. Critically, it is shown that the latter is extremely efficient at inhibiting the generation of optically‐active VB− centers. This is significant because foreign atoms such as carbon are commonplace on both the top and bottom surfaces of hBN during ion irradiation, in the form of hydrocarbon contaminants, polymer residues from hBN transfer methods, protective capping layers and substrates. Recoil implantation must be accounted for when selecting ion beam parameters such as ion mass, energy, fluence, incidence angle, and sputter/span yield, which are discussed in the context of a framework for VB− generation by high‐resolution focused ion beam (FIB) systems.

(Invited) Considerations in Sample Environment and Data Processing for Operando Cell Studies by Neutron Depth Profiling

Neutron depth profiling (NDP) is a nominally non-destructive analytical technique used to measure select isotopes (6Li, 14N, 10B, etc...) in a diversity of materials. NDP can be conducted on operating Li-ion cells and be used to provide researchers real-time information about cell formation, conductance, and resilience. The increased use of NDP for electrochemical studies within the past decade has inspired the development of new sample preparation and data reduction strategies. Select topics that have been studied in the U.S. have included issues of neutron attenuation and scattering due to the addition of a protective capping layer over a cell, the possible need for matrix matched standards for complex materials, and the streamlining of the NDP data reduction procedure. Several challenges remain, however, including improving NDP data acquisition and reduction methods for detectable, low-Z isotopes such as 14N and 35Cl and improving upon the NDP data reduction and processing procedures so that they are more accessible to non-instrument specialists. All these topics will be discussed in this presentation.

Study of the temporal stability of the reflection coefficient in the vicinity of 58.4 nm of narrow-band Sc/Al mirrors with Si or ScNx interlayers and a MoSi2 protective cap layer

Observation of a sample of Si/Al/Sc mirror with a MoSi2 protective cap layer, which was stored in air for 40 months, showed that the peak reflectivity at a wavelength of 58.4 nm during this period decreased from 32 % to 20.5 %, and over the last 20 months of observation—from 21.5 % to 20.5 %, which indicates a significant decrease in the rate of decline and almost stabilization of the peak reflectivity at the level of 20 %. The spectral reflection peak width of this mirror at half maximum has not changed over the past 20 months and amounted to 6.3 nm. The given data of secondary ion mass spectrometry and grazing incidence X-ray reflectometry show that the decrease in reflectance of Si/Al/Sc multilayer mirrors with a MoSi2 protective cap layer is mainly due to an increase in the amount of impurities (oxygen and carbon) in the structure and on the surface of the mirrors and, to a lesser extent, due to the broadening of the interlayer boundaries. Comparison of the rate of decrease in reflectance at 58.4 nm of Sc/Al mirrors with interlayers of silicon and nitride scandium and a MoSi2 cap layer indicates that neither the material and thickness of the interlayer nor the thickness of the protective MoSi2 cap layer within 3–6 nm have a significant effect on this rate.

Investigation of gap states near conduction band edge in vicinity of interface between Mg-ion-implanted GaN and Al2O3 deposited after ultra-high-pressure annealing

The gap states near the conduction band edge (E C) in the vicinity of the interface between Mg-ion-implanted GaN and Al2O3 deposited after post-implantation annealing were investigated in the range between E C – 0.15 eV and E C – 0.45 eV. For this purpose, capacitance–voltage measurements were performed on MOS diodes with the n-type conduction of Mg-implanted GaN maintained by suppressing the dose. Although the gap state density D T was reduced for the sample prepared with the dose of 1.5 × 1012 cm–2 by conventional rapid thermal annealing (RTA) at 1250 °C for 1 min using an AlN protective cap layer, further improvement was achieved by capless ultra-high-pressure annealing (UHPA) at the same temperature for the same duration. Furthermore, the D T distributions for the samples with capless UHPA at 1400 °C for 5 min are comparable to that for the sample with conventional RTA at 1250 °C for 1 min using the cap layer.

Strain engineering in 2D hBN and graphene with evaporated thin film stressors

We demonstrate a technique to strain two-dimensional hexagonal boron nitride (hBN) and graphene by depositing stressed thin films to encapsulate exfoliated flakes. We choose optically transparent stressors to be able to analyze strain in 2D flakes through Raman spectroscopy. Combining thickness-dependent analyses of Raman peak shifts with atomistic simulations of hBN and graphene, we can explore layer-by-layer strain transfer in these materials. hBN and graphene show strain transfer into the top four and two layers of multilayer flakes, respectively. hBN has been widely used as a protective capping layer for other 2D materials, while graphene has been used as a top gate layer in various applications. Findings of this work suggest that straining 2D heterostructures with evaporated stressed thin films through the hBN capping layer or graphene top contact is possible since strain is not limited to a single layer.

Study of ruthenium film grown in oxygen environment for x-ray optics application

Ru shows high damage threshold as compared to other standard materials Au, Rh and Pt for high heat load applications in high brilliance synchrotron radiation source and x-ray free electron laser. It is also a promising candidate to be used as a protective capping layer in multilayers for increasing their life time. In the present study, Ru thin films of 500Å thickness were deposited in oxygen environment at different substrate temperatures varying from 70°C to 500°C. In reactive ion beam sputtering process, the flow of Ar and reactive O2 gas was maintained in 4:1 ratio keeping total flow 3 SCCM constant. The deposited films were characterized using grazing incidence x-ray reflectivity (GIXRR), grazing incidence x-ray diffraction (GIXRD) and secondary ion mass spectroscopy (SIMS) techniques. A significant change in GIXRR profile was observed in the sample grown at 100°C and 500°C whereas the GIXRD measurements indicated no significant formation of ruthenium oxide at different temperatures. However, a strong peak of Ru2Si3 (222) at 500°C was observed indicating a strong interfacial reaction at ruthenium/ substrate interface.The experimental data suggested a weak signature of RuO2 phase in the films deposited at RT, 70°C and 100°C and therefore the effect of ruthenium oxide with 10% composition in pure ruthenium was calculated on optical performance in extreme ultra violet region of photon energy (85-115 eV).

Interface Engineering Enabled Low Temperature Growth of Magnetic Insulator on Topological Insulator

AbstractCombining topological insulators (TIs) and magnetic materials in heterostructures is crucial for advancing spin‐based electronics. Magnetic insulators (MIs) can be deposited on TIs using the spin‐spray process, which is a unique nonvacuum, low‐temperature growth process. TIs have highly reactive surfaces that oxidize upon exposure to atmosphere, making it challenging to grow spin‐spray ferrites on TIs. In this work, it is demonstrated that a thin titanium capping layer on TI, followed by oxidation in atmosphere to produce a thin TiOx interfacial layer, protects the TI surface, without significantly compromising spin transport from the magnetic material across the TiOx to the TI surface states. First, it is demonstrated that in Bi2Te3/TiOx/Ni80Fe20 heterostructures, TiOx provides an excellent barrier against diffusion of magnetic species, yet maintains a large spin‐pumping effect. Second, the TiOx is also used as a protective capping layer on Bi2Te3, followed by the spin‐spray growth of the MI, NixZnyFe2O4 (NZFO). For the thinnest TiOx barriers, Bi2Te3/TiOx/NZFO samples have antiferromagnetic (AFM) disordered interfacial layer because of diffusion. With increasing TiOx barrier thickness, the diffusion is reduced, but still maintains strong interfacial magnetic exchange‐interaction. These experimental results demonstrate a novel method of low‐temperature growth of magnetic insulators on TIs enabled by interface engineering.

Stabilization of the oxygen concentration in La0.3Sr0.7CoO3−δ thin films by 3 nm thin LaAlO3 capping layer

We prepared La0.3Sr0.7CoO3−δ thin films by pulsed laser deposition on (LaAlO3)0.3(Sr2TaAlO6)0.7 substrates with and without a protective LaAlO3 capping layer and investigated their structural and magnetic properties. We observed that, in the uncapped films, the Curie temperature strongly decreased after annealing in helium atmosphere, and it significantly decreased even in samples stored for several weeks at room temperature. The decrease of the Currie temperature is caused by an increase of the concentration of oxygen vacancies, δ. However, we show that already a 3 nm thin LaAlO3 capping layer can essentially conserve δ at room temperature, and it considerably slows down the formation of oxygen vacancies at elevated temperatures.

Lasing below 170 nm using an oscillator FEL

The short wavelength operation of free-electron laser (FEL) oscillators is limited by the availability of high-reflectivity, thermally stable, and radiation-resistant FEL mirrors in the vacuum UV (VUV) wavelength. We report our recent work to extend the shortest lasing wavelength of the oscillator FEL to 168.6 nm using a storage ring FEL. This progress has been made possible by developing a new FEL configuration with substantially reduced undulator harmonic radiation on the FEL mirror, a thermally stable FEL optical cavity, and a new type of high-reflectivity fluoride-based multilayer coating with a protective capping layer. Using these fluoride-based mirrors, we have demonstrated storage ring FEL lasing from 168.6 to 179.7 nm with excellent beam stability. Employing this VUV FEL in Compton scattering, we have produced the first 120 MeV gamma rays at the High Intensity Gamma-ray Source (HIGS). Operating the HIGS in this new high-energy region will create many new opportunities for photonuclear physics research, in particular, the low-energy quantum chromodynamics research.

The Role of the Atmosphere on the Photophysics of Ligand‐Free Lead‐Halide Perovskite Nanocrystals

AbstractLead halide perovskite (LHP) nanocrystals (NCs) have gained attention over the past decade due to their outstanding optoelectronic properties, making them a suitable material for efficient photovoltaic and light emitting devices. Due to its soft nature, these nanostructures undergo strong structural changes upon irradiation, where these light‐induced processes are strongly influenced by the environment. Since most processing routes for LHP NCs are based on colloidal approaches, the role of factors such as stabilizing ligands or solvents is usually hard to disentangle from the interaction of external radiation with the perovskite material. Employing a recently proposed synthetic approach, where ligand‐free NCs can be grown within metal‐oxide‐based insulating nanoporous matrices, it has been feasible to perform a clean study of the effect of the surrounding atmosphere on the photophysical properties of perovskite NCs, avoiding the interference of protective capping layers or solvents. Simultaneous light‐induced photo‐activation and darkening processes are monitored and disentangled, and their relation with bulk and surface processes, respectively, demonstrated.

Surface Chemistry Matters: How Ligands Influence Excited State Interactions between CsPbBr3 and Methyl Viologen

The photocatalytic properties of cesium lead bromide (CsPbBr3) perovskite nanocrystals make them attractive for designing light harvesting assemblies. Often ignored, the surface chemistry can dictate the excited state interactions of these semiconductor nanocrystals with charge-shuttling redox molecules. We have now explored the impact of CsPbBr3 nanocrystal surface modification on the excited state interactions with methyl viologen (MV2+) for three different ligand environments: prototypical oleic acid/oleylamine (OA/OAm) ligands, PbSO4-oleate capping, and didodecyldimethylammonium bromide (DDAB) ligands. Native OA/OAm ligands and PbSO4-oleate capping exhibit the strongest complexation with MV2+, whereas the bulky DDAB ligand environment shows an order of magnitude weaker complexation. The electron transfer rate constants as measured from transient absorption spectroscopy vary in the range of 1.2–3.6 × 1011 s–1 for different ligand environments. For DDAB-CsPbBr3 NCs, the efficiency of electron transfer (Φet) is 73%. Despite a protective capping layer, PbSO4-oleate capped CsPbBr3 maintains a redox-active surface which is viable for photocatalytic applications. These results highlight the impact of surface chemistry on excited state interactions of CsPbBr3 NCs and photocatalytic applications. Figure 1

Effects of ultra-high-pressure annealing on characteristics of vacancies in Mg-implanted GaN studied using a monoenergetic positron beam

Vacancy-type defects in Mg-implanted GaN were probed by using a monoenergetic positron beam. Mg ions were implanted into GaN to obtain 0.3-μm-deep box profiles with Mg concentrations of 1 × 1019 cm−3. The major defect species in an as-implanted sample was determined to be Ga-vacancy related defects such as a complex between Ga and N vacancies. The sample was annealed under a nitrogen pressure of 1 GPa in a temperature range of 1000–1480 °C without a protective capping layer. Compared with the results for Mg-implanted GaN annealed with an AlN capping layer, the defect concentration was decreased by the cap-less annealing, suggesting that the surface of the sample was an effective sink for vacancies migrating toward the surface. Depth distributions of Mg after annealing above 1300 °C were influenced by the presence of residual vacancies at this temperature. Hydrogen atoms were unintentionally incorporated into the sample during annealing, and their diffusion properties were also affected by both vacancies and Mg.

Applications of Casimir forces: Nanoscale actuation and adhesion

Here, we discuss possible applications of the Casimir forces in micro- and nanosystems. The main part of this paper is devoted to actuation with quantum fluctuations and to the relative contribution of van der Waals and Casimir interactions to adhesion. Switching between the amorphous and crystalline states of phase change materials could generate force contrast sufficient for actuation, though for practical applications, the influence of protective capping layers and volume compression have to be better understood. Resilience against the pull-in instability is also a critical point defined by the material choice, dissipation in the system, and roughness of the surfaces. The adhesion induced by the Casimir forces is omnipresent, and it can play a pivotal role in unwanted stiction demanding deeper understanding. The open problems are the distance upon contact and the relative area of the real contact since both of them control the adhesion. An experiment designed to answer these questions is briefly discussed.

Effect of the surface oxide layer on the stability of black phosphorus

It has been a long-standing challenge to produce air-stable few-layer black phosphorus (BP) because BP degrade rapidly in ambient atmosphere. Here we demonstrate that the pristine BP with ten layers or more possesses a strong stability and can be stored in air for two weeks. The physical mechanism can be ascribed to the native phosphorus oxide formed on the surface, which act as a stable and protective capping layer and prevent the underlying layer from further oxidation. The pristine 10-layer BP FET device can maintain a high mobility value of around 220 cm2 V-1s−1 in air for 2 weeks. By contrast, the plasma-induced phosphorus oxide is not dense or robust enough to protect the underlying sample from oxidation. These results suggest that the density of the oxide layer on the surface plays a vital role in the stability of BP flakes. This work offers new perspectives for probing the stability of BP based electronic and optoelectronic devices.

Coherent growth and characterization of van der Waals 1T−VSe2 layers on GaAs(111)B using molecular beam epitaxy

We report epitaxial growth of vanadium diselenide (VSe$_2$) thin films in the octahedrally-coordinated (1T) structure on GaAs(111)B substrates by molecular beam epitaxy. Film thickness from a single monolayer (ML) up to 30 ML is demonstrated. Structural and chemical studies using by x-ray diffraction, transmission electron microscopy, scanning tunneling microscopy and x-ray photoelectron spectroscopy indicate high quality thin films. Further studies show that monolayer VSe$_2$ films on GaAs are not air-stable and are susceptible to oxidation within a matter of hours, which indicates that a protective capping layer should be employed for device applications. This work demonstrates that VSe$_2$, a candidate van der Waals material for possible spintronic and electronic applications, can be integrated with III-V semiconductors via epitaxial growth for 2D/3D hybrid devices.