Ultrathin Layer Research Articles

Atomic Layer-Deposited Silane Coupling Agent for Interface Passivation of Quantum Dot Light-Emitting Diodes.

Inserting an insulating layer between the charge transport layer (CTL) and quantum dot emitting layer (QDL) is widely used in improving the performance of quantum dot light-emitting diodes (QLEDs). However, the additional layer inevitably leads to energy loss and joule heat. Herein, a monolayer silane coupling agent is used to modify the said interfaces via the self-limiting adsorption effect. Because the ultrathin layers induce negligible series resistance to the device, they can partially passivate the interfacial defects on the electron transport side and help confine the electrons within the QDL on the hole transport side. These interfacial modifications can not only suppress the nonradiative recombination but also slow down the aging of the hole transport layer. The findings here underline a low-temperature adsorption-based strategy for effective interfacial modification which can be used in any layer-by-layer device structures.

Hybrid Nanogel-Wrapped Anisotropic Gold Nanoparticles Feature Enhanced Photothermal Stability.

Anisotropic gold nanoparticles (AuNPs) are renowned for their unique properties - including localized surface plasmon resonance (LSPR) and adjustable optical responses to light exposure - that enable the conversion of light into heat and make them a promising tool in cancer therapy. Nonetheless, their tendency to aggregate and consequently lose their photothermal conversion capacity during prolonged irradiation periods represents a central challenge in developing anisotropic AuNPs for clinical use. To overcome this issue, an innovative approach that facilitates the encapsulation of individual anisotropic AuNPs within thin nanogels, forming hybrid nanomaterials that mirror the inorganic core's morphology while introducing a negligible (2-8nm) increase in overall diameter is proposed. The encapsulation of rod- and star-shaped anisotropic AuNPs within poly-acrylamide (pAA) or poly-(N-isopropylacrylamide) (pNIPAM) nanogels is successfully demonstrated. The ultrathin polymeric layers display remarkable durability, significantly enhancing the photothermal stability of anisotropic AuNPs during their interaction with near-infrared light and effectively boosting their photothermal capacities for extended irradiation periods. The outcomes of the research thus support the development of more stable and reliable AuNPs as hybrid nanomaterials, positioning them as promising nanomedicinal platforms.

Identifying Root Origin of Insulating Polymer Mediated Solar Water Oxidation.

Rational construction of high-efficiency photoelectrodes with optimized carrier migration to the ideal active sites, is crucial for enhancing solar water oxidation. However, complexity in precisely modulating interface configuration and directional charge transfer pathways retards the design of robust and stable artificial photosystems. Herein, a straightforward yet effective strategy is developed for compact encapsulation of metal oxides (MOs) with an ultrathin non-conjugated polymer layer to modulate interfacial charge migration and separation. By periodically coating highly ordered TiO2 nanoarrays with oppositely charged polyelectrolyte of poly(dimethyl diallyl ammonium chloride) (PDDA), MOs/polymer composite photoanodes are readily fabricated under ambient conditions. It is verified that electrons photogenerated from the MOs substrate can be efficiently extracted by the ultrathin solid insulating PDDA layer, significantly boosting the carrier transport kinetics and enhancing charge separation of MOs, and thus triggering a remarkable enhancement in the solar water oxidation performance. The origins of the unexpected electron-withdrawing capability of such non-conjugated insulating polymer are unambiguously uncovered, and the scenario occurring at the interface of hybrid photoelectrodes is elucidated. The work would reinforce the fundamental understanding on the origins of generic charge transport capability of insulating polymer and benefit potential wide-spread utilization of insulating polymers as co-catalysts for solar energy conversion.

Engineering of Co/MgO interface with combination of ultrathin heavy metal insertion and post-oxidation for voltage-controlled magnetic anisotropy effect

The voltage-controlled magnetic anisotropy (VCMA) effect in ferromagnet/insulator junctions provides an effective way to manipulate electron spins, which can form the basis of future magnetic memory technologies. Recent studies have revealed that the VCMA effect can be strongly tuned by a process of “interface engineering” exploiting ultrathin heavy metal layers and an electron depletion effect. To further decrease the numbers of electrons, chemical reactions, such as surface oxidation of ferromagnets, may also be an effective way to achieve this depletion. However, the knowledge of combined effect of heavy metal layers and oxidation is still lacking. Here, we demonstrate that dual interfacial engineering using an insertion of heavy metals (Pt or Re) and a post-oxidation process can have a remarkable effect on the perpendicular magnetic anisotropy and the VCMA effect. Interestingly, a strong enhancement of the perpendicular magnetic anisotropy is observed by dual interfacial engineering with Pt insertion, although it does not occur with Pt insertion or surface oxidation alone. Furthermore, even a sign reversal of the additional VCMA effect due to the ultrathin heavy metal layers is observed by utilizing dual interfacial engineering. These findings provide another degree of freedom for designing voltage-controlled spintronic devices and pave the way to interfacial spin–orbit engineering for the VCMA effect.

On the Topotactic Phase Transition Achieving Superconducting Infinite-Layer Nickelates.

Topotactic reduction is critical to a wealth of phase transitions of current interest, including synthesis of the superconducting nickelate Nd0.8Sr0.2NiO2, reduced from the initial Nd0.8Sr0.2NiO3/SrTiO3 heterostructure. Due to the highly sensitive and often damaging nature of the topotactic reduction, however, only a handful of research groups have been able to reproduce the superconductivity results. A series of in situ synchrotron-based investigations reveal that this is due to the necessary formation of an initial, ultrathin layer at the Nd0.8Sr0.2NiO3 surface that helps to mediate the introduction of hydrogen into the film such that apical oxygens are first removed from the Nd0.8Sr0.2NiO3 / SrTiO3 (001) interface and delivered into the reducing environment. This allows the square-planar / perovskite interface to stabilize and propagate from the bottom to the top of the film without the formation of interphase defects. Importantly, neither geometric rotations in the square planar structure nor significant incorporation of hydrogen within the films is detected, obviating its need for superconductivity. These findings unveil the structural basis underlying the transformation pathway and provide important guidance on achieving the superconducting phase in reduced nickelatesystems.

Plasma surface treatment of amorphous Ga2O3 thin films for solar-blind ultraviolet photodetectors

Recently, amorphous gallium oxide (a-Ga2O3) thin films are gaining more and more attention due to their advantages of low cost and low temperature growth. However, a-Ga2O3 solar-blind ultraviolet photodetectors are plagued by issues such as slow response speed and high dark current. In this work, radio frequency magnetron sputtering was used for a-Ga2O3 deposition, and a novel approach of plasma treatment (including oxygen, argon and hydrogen plasmas) was employed to tailor the device performance using a plasma-enhanced chemical vapor deposition system. It is demonstrated that: (i) the oxygen atoms and ions in the oxygen plasma effectively reduce the oxygen vacancy concentration and improve the respond speed of a-Ga2O3 photodetectors; (ii) the argon ions in the argon plasma create additional defects (such as dangling bonds and oxygen vacancies) and improve the responsivity of a-Ga2O3 photodetectors; (iii) the hydrogen atoms in the hydrogen plasma may incorporate into the film and form an ultra-thin passivation layer near the surface, which gives rise to a balance between responsivity and response speed. Finally, through the detailed analysis of the optical emission spectra and photoelectric performance, the underlying physical mechanism based on the energy band diagram has been proposed to interpret the obtained experimental results.

Improvement of voltage-controlled magnetic anisotropy effect by inserting an ultrathin metal capping layer

Improvement of voltage-controlled magnetic anisotropy effect by inserting an ultrathin metal capping layer

Mid-infrared photodetector spectrometer concept based on ultrathin all-dielectric metamaterial with azimuth-incidence-angle tuned perfect optical absorption: Design and analysis

Novel concepts for efficient compact spectroscopy are extensively researched due to their fundamental applications in prominent fields such as chemistry, biology, and physics. Here, with an unprecedented spectral-azimuthal resolution, such a concept is introduced and exemplified in the mid-infrared, in which its advantages are paramount and have yet to be established industrially. The concept is based on the design and instrumentation of optical absorption spectral tuning (or sensitivity) to the relative azimuthal component of light impinging on specifically designed metamaterials (MMs). The inversely-designed MMs offer perfect photo-absorption inside λ0/200 ultra-thin layer of lead telluride. Two small-footprint system designs are proposed to instrument the spectral-azimuth-angle tuning for spectrometry. The first is based on a single or few spinning MM layout elements, and the second, to avoid spinning, utilizes a fixed focal-plane-array approach. The latter exploits the inherent variations in the local azimuthal-incidence angle. While low absorption is the Achilles heel of conventional mid-infrared photodetector spectrometers, the optimized MMs, besides their unique spectral-azimuth-angle tuning functionality, provide giant absorption enhancement, facilitating higher resolution and even smaller in-plane form factor. The highlighted concept opens an additional dimension to encode-decode spectral information, yielding profound advantages over conventional designs, such as those based on diffraction gratings.

Substrate‐Free Terahertz Metamaterial Sensors With Customizable Configuration and High Performance

AbstractMetamaterials based on quasi‐bound states in the continuum (qBICs) with manipulable resonance quality (Q) factors have provided a standout platform for cutting‐edge terahertz (THz) sensing applications. However, most so far have been implemented as conventional metal patch structures with adjacent substrate layers, incurring the limitation of insufficient light‐matter interaction due to substrate effects. Here, qBIC‐driven metamaterials with substrate‐free metallic aperture structures for tailoring light‐matter interactions and exhibiting near‐ideal sensing performance is introduced. Specifically, it is incorporated ultrafast femtosecond laser processing technology to fabricate H‐type metallic aperture metamaterials with accessible high‐contrast Q factor resonances allowed by in‐plane symmetry breaking. Correspondingly, stronger light field energies are applied to the interactions due to completely eliminating the confinement of the substrate effect, enabling experimental sensitivity of up to 0.86 THz RIU−1 for the qBIC resonance, 1.9 times that of the conventional dipole resonance. Moreover, a high Q qBIC resonance achieved by optimized asymmetry parameter is exploited for detecting ultrathin layers of L‐proline molecules as low as 0.87 nmol. It is envisioned that this approach will deliver insights for real‐time, precise, and high‐performance detection of trace biomolecules, and open new perspectives for realizing ideal performance metadevices.

Enhanced Antifouling Capability of In Situ-Grown Hydrophilic-Hydrophobic Nanodomains on Membrane Surface in the Ultralow Pressurized Ultrafiltration Process.

Although hydrophilic modification of the membrane surface is widely adopted, polymeric membranes still suffer from irreversible fouling caused by hydrophilic components in surface water. Here, an ultrathin hydrogel layer (40 nm) with hydrophilic-hydrophobic textures was in situ grown onto the polysulfone ultrafiltration membrane surface using an organic-radical-initiated interfacial polymerization technique. The interfacial polymerization of hydrophilic and hydrophobic monomers ensured the molecular-scale distribution of hydrophilic and hydrophobic nanodomains on the membrane surface. These nanodomains, with their molecular lengths, facilitated dynamic repulsion interactions between the uniformly textured surface and foulant components with different degrees of hydrophilicity. Chemical force characterization confirmed that the adhesion force between the hydrophilic-hydrophobic textured membrane surface and foulants (dodecane, bovine serum albumin, and humic acid) was greatly reduced. Dynamic filtration experiments showed that a hydrophilic-hydrophobic textured membrane always possessed the largest water flux and the best antifouling performance. Furthermore, the foulant coverage ratio on the membrane surface was first evaluated by measuring changes in surface streaming potentials, which demonstrated a 69% reduction in the amount of foulant adhering to the hydrophilic-hydrophobic textured membrane surface. Therefore, the construction of hydrophilic-hydrophobic nanodomains on the membrane surface provides a promising strategy for alleviating membrane fouling caused by both hydrophobic and hydrophilic components during ultralow pressurized ultrafiltration processes.

Hydrogenation by catalytically generated atomic hydrogen for passivating contacts in crystalline silicon solar cells

Hydrogenation employing catalytically generated atomic hydrogen (Cat-H) is implemented on stacks of n-type polycrystalline silicon (poly-Si)/Si oxide (SiOx) to enhance passivation quality. The utilization of Cat-H demonstrates a substantial enhancement in surface passivation quality on crystalline Si (c-Si), resulting in an increase of the effective minority carrier lifetime (τeff) from 2.0 to 3.9 ms. The investigation reveals a dependency of τeff on the duration of Cat-H treatment: an initial rise followed by a plateau or slight decline. Secondary ion mass spectrometry (SIMS) measurements revealed the diffusion of H atoms into poly-Si and c-Si, which accumulate at the poly-Si/c-Si interface. This accumulation terminates dangling bonds in the poly-Si layer on the c-Si surface. Furthermore, the presence of an ultra-thin thermal Si oxide layer on the poly-Si layer formed during high-temperature annealing is crucial for protecting the film against etching induced by Cat-H.

Improved electron transport in planar perovskite solar cells using TiO2, SnO2 and WO3 ultra-thin layers: a comparison on all single layer and bilayer structures

Improved electron transport in planar perovskite solar cells using TiO2, SnO2 and WO3 ultra-thin layers: a comparison on all single layer and bilayer structures

Modulation of π-Electron Density in Ultrathin 2D Layers of Graphite Carbon Nitride for Efficient Photocatalytic Hydrogen Production.

The rational design and synthesis of novel semiconductor nano-/quantum materials have been ambitiously pursued in the field of photocatalysis as the technology is promising and critical for attaining future energy and environmental sustainability. Herein, the integrity of aromatic carbon into graphitic carbon nitride (CN) at the same molecular plane with a few 2D layers is achieved by using modulated precursors of CN, forming carbon regulated ultrathin CN (CUCN) with improved charge transfer kinetics and photocatalytic hydrogen production. The grafted graphite rings adjacent to carbon nitride frameworks induce a significant rearrangement and relocalization of the overall framework, and form conjugated sp2 hybridized interfaces and internal electric fields that drive the separation and directional transfer of photogenerated electrons from CN sheets towards intralayer graphite regions, where the photocatalytic hydrogen evolution reaction occurs extensively, yielding largely increased HER rate of 2231.8 µmol g-1 h-1 by 8.2 times relative to CN, as well as a remarkable apparent quantum yield of 2.93% under monochromatic light at 420 nm. The high physicochemical stability and low synthesis cost of CUCN make it a potential benchmark photocatalyst that can be readily modified via element doping, heterojunction introduction, defect engineering, and so on, to further enhance its HER performance.

Bis-tris-based polyester nanofiltration membranes fabricated via one-step interfacial polymerization for desalination

To obtain high-performance polyester (PE) nanofiltration (NF) membranes for desalination, most PE NF membranes are fabricated with high aqueous monomer concentration, or high reaction temperature, or long reaction time. The interfacial polymerization (IP) reaction rate between hydroxyl groups and acyl chloride groups is promoted but the cost of membrane fabrication is also increased. In this work, Bis-tris (bis(2-hydroxyethyl)-amino-tris(hydroxymethyl)methane) with rich hydroxyl groups is first utilized as an aqueous monomer to fabricate PE membranes under conventional IP conditions. The fabricated Bis-tris PE membranes feature strong hydrophilicity, excellent electronegativity, and ultra-thin selective layers, which are conducive to improving desalination performance. The optimized Bis-tris PE membrane shows excellent water permeance of 22.5 L m−2 h−1 bar−1 and a satisfactory Na2SO4 rejection of 96.9 %. Additionally, the Bis-tris PE membrane displays superior long-term stability and chlorine resistance under 96 h cross-flow filtration. This research enlightens the promising potential of Bis-tris as a novel and economic aqueous monomer for the fabrication of high-performance PE NF membranes.

Ultrathin titanium carbide-modified separator for high-performance lithium–sulfur batteries

Despite a high theoretical capacity, the practical application of lithium-sulfur batteries has been primarily limited by the migration of long-chained polysulfide species during the charge/discharge processes. One effective approach to address the issues is to design a functional separator or interlayer. Here, we prepared a modified separator with an ultrathin layer of titanium carbide (TiC) using radio-frequency sputtering on a commercial Celgard polypropylene membrane. The 240-nm TiC coating layer can enhance the interfacial properties of Celgard separators in porosity, wettability, roughness, etc. Hence, via experimental and theoretical investigation, we discovered that TiC can efficiently adsorb polysulfides and boost charge transfer via strong covalent C–S bonds. Using a TiC-modified separator can impede the shuttle effect and improve the kinetics of sulfur conversion reactions. Thus, the Li–S batteries with TiC separator deliver excellent electrochemical performances with a good rate capability (717 mAh g−1 at 7.0C) and an ultra-low decay rate of 0.058 % per cycle over 800 cycles at a C-rate of 2.0C. Furthermore, a high areal capacity of 4.3 mAh cm−2 was achieved with a high mass-loading of sulfur cathode up to 7.0 mg cm−2.

Starfish-inspired ultrasensitive piezoresistive pressure sensor with an ultra-wide detection range for healthcare and intelligent production

Flexible pressure sensors have attracted significant attention due to their wide range of applications in various fields (e.g., robotis, healthcare, and human–machine interfaces). However, achieving both high sensitivity and a wide detection range remains a challenge. Here, we propose a novel starfish-inspired ultrasensitive piezoresistive pressure sensor capable of detecting an extensive range of pressures. The sensor’s design incorporates high and low spine structures inspired by the surface of a starfish, efficiently preventing rapid saturation of detection range and expanding the response range. Unlike single-material nanofiber structures, the ultrathin and ultrasensitive layer, fabricated using PEDOT: PSS/TPU nanofibers, possesses a large surface area ratio and numerous contact points. This allows for a quick increase in conductive channels when pressure is applied. The intertwining of PEDOT: PSS fibers with TPU fibers enhances both the mechanical strength of the fiber membrane and the initial resistance of the sensor, thereby increasing its sensitivity. Additionally, PVA fibers are fabricated over the interdigital electrode to serve as insulation layer for controlling resistance change between the sensitive layer and the electrode. Importantly, the interaction between the PVA fibers and the PEDOT: PSS/TPU fibers alters the deformation behavior of the sensitive layer fibers, further enhancing the performance of the sensor. The fabricated sensor demonstrates exceptional sensitivity (302.9 kPa−1), an extensive detection range of 0–426.7 kPa, and remarkable endurance of over 7,000 cycles at 110 kPa, rendering it a device with great potential for precise pressure sensing applications in health monitoring and intelligent production.

Piezoelectric assisted boosting photocatalytic hydrogen evolution over a finely prepared Pt/TiO2/g-C3N4 composite system using lactic acid as sacrificial agent

A one-step calcination method was employed to fabricate a new TiO2/g-C3N4(TCN) composite catalyst. The therein TiO2 nanoparticles with good dispersion were synthesized through a sol-gel method and followed by additional heat treatment. The ultra-thin and flat g-C3N4(CN) nanosheets were synthesized by calcining a mixture of urea and melamine. The obtained TCN exhibited significantly excellent performance, especially when 3 wt% Pt was added and lactic acid (HL) was used as a sacrificial agent, achieving a rate of 32.5 mmol/h/g. This improvement can be attributed to the uniform dispersion of nano TiO2 particles on g-C3N4, the flat ultra-thin layer structure of CN, and the constructed heterojunctions between two, which promote the separation of photogenerated electron-hole pairs. Measurements of PL and photocurrent response confirmed enhanced efficiency in interface charge separation and transfer. Additionally, it demonstrated lower internal resistance in EIS tests. Notably, owing to the piezoelectric properties of CN, when the reaction liquid was subjected to additional ultrasonic treatment, the hydrogen production rate further increased to 43.57 mmol/h/g and 2.9 mmol/h/g, respectively, in simulated sunlight and visible light response. The piezoelectric effect of CN induced by ultrasound regulated the bandgap width of the catalysts, broadening their response to visible light.

On the role of ultrathin lithium metal anodes produced by thermal evaporation

Lithium metal anodes (LMAs) are the preferred option for the next generation of lithium batteries, where high energy density and longer cycle life are required. A new battery design eliminating the LMA in the discharged state provides the highest achievable energy density with reduced safety hazards, though irreversible Li losses impede the practical application of the anode-free concept. In this work, by using an ultrathin layer (<5 μm) of lithium, which is deposited by thermal evaporation on copper current collectors, a reduction on the energy barrier of lithium nucleation during the plating process is demonstrated. Furthermore, the metallic lithium deposited over the charge step provides a homogeneous layer, fairly reducing the dendritic growth and the generation of dead lithium. Finally, a functional solid electrolyte interphase (SEI) with Li2O and LiOH as predominant species, gives greater protection to the anode/electrolyte interface, leading to a more stable cycling of the battery. These insights provide a solid starting point for future studies that may lead to practical design changes to improve stability and extend the battery life of lithium metal batteries.

Boundary-induced phase in epitaxial iron layers

We report on the discovery of a boundary-induced body-centered tetragonal iron phase in thin films deposited on MgAl2O4 (001) substrates. We present evidence for this phase using detailed x-ray analysis and density functional theory calculations. A lower magnetic moment and a rotation of the easy magnetization direction are observed, as compared with body-centered cubic iron. Our findings expand the range of known crystal and magnetic phases of iron, providing valuable insights for the development of heterostructure devices using ultrathin iron layers. Published by the American Physical Society 2024

All-dielectric meta-surface transmission-mode ultra-thin GaAs negative electron affinity photocathode

Transmission-mode (t-mode) GaAs negative electron affinity photocathodes (NEA-PCs) can be integrated with the optical focusing lenses and microchannel plates to produce high-quality electron beams and high-sensitive detectors. Quantum efficiency (QE) of ∼40% has been reported for the t-mode thick (&amp;gt;1000 nm) GaAs NEA-PCs. Nevertheless, practical applications of these devices have been seriously restricted by their long response time (tens of picoseconds). In this work, the all-dielectric meta-surfaces (ADMS) were designed as the light managers for the t-mode ultra-thin GaAs NEA-PCs. For the 500–850 nm waveband, high light absorption (&amp;gt;80%) can be obtained through coupling the electromagnetic dipole moments of ADMS into the leaky optical modes in 100 nm ultra-thin GaAs NEA-PC layer, which leads to enhanced QE higher than that of the thick ones, the response time less than 5 ps, and the mean transverse energy less than 60 meV, respectively. Given these properties, ADMS t-model ultra-thin NEA-PCs represent a promising photocathode to provide the high-brightness short-pulse spin-polarized electron beams and high-sensitive fast-response detectors for the electron accelerator and low-light-level photodetection applications, respectively.