Ultrathin Films Research Articles

Quantitative Eliashberg theory of the superconductivity of thin films.

A quantitative theory of the superconductivity of materials confined at the nanoscale in parameter-free agreement with experimental data has been missing so far.
We present a generalization, in the Eliashberg framework, of a BCS theory of superconductivity in good metals which are confined along one of the three spatial directions, such as thin films. In this formulation of the Eliashberg equations the approximation of taking the normal density of states (DOS) as its value at the Fermi level has been removed. By numerically solving these new Eliashberg-type equations, we find the dependence of the superconducting critical temperature $T_{c}$ on the confinement size $L$, in quantitative agreement with experimental data of Pb and Al thin films with no adjustable parameters. This quantitative agreement provides an indirect confirmation that, upon increasing the confinement, a crossover from a spherical-like Fermi surface, which contains two growing hole pockets caused by the confinement, to a strongly deformed Fermi surface, occurs. This topology of the Fermi sea is implemented in the new Eliashberg-type equations to reproduce the experimentally observed maximum in the critical superconducting temperature vs film thickness of ultra-thin Pb films.

Nanofiltration Membrane with Enhanced Ion Selectivity Based on a Precision-Engineered Ultrathin Polyethylene Supporting Layer.

Nanofiltration (NF) technology is increasingly used in the water treatment and separation fields. However, most research has focused on refining the selective layer while overlooking the potential role of the supporting layer. With expertise in ultrathin polymer films, particularly in the production of polyethylene (PE) membranes, we explore the possibility of improving NF membrane performance by precisely controlling the structure and surface properties of the ultrathin supporting layer in this work. Here, we introduced an innovative NF membrane that used a submicrometer ultrathin PE membrane produced through a biaxial stretching process, which is significantly thinner than commercial PE membranes available on the market. The core innovations are as follows: first, we focused on precise control of the supporting layer rather than just the selective layer, achieving significant enhancements in overall NF membrane performance; second, the ultrathin PE supporting layer served as a tunable interface for interfacial polymerization, offering possibilities for structural control of the selective layer and advancing membrane performance innovations. The resulting NF membrane boasts an overall thickness of ∼630 nm, which represents the thinnest NF membrane documented to date. This ultrathin NF membrane showed an ultrahigh Cl-/SO42- selectivity of 338.03, placing it at the forefront of existing literature. This study sheds light on the important role of the supporting layer in the preparation of selective layers. We believe that this approach has the potential to contribute to the development of ultrathin, high-performance NF membranes.

Prospects of Improving Efficiency and Stability of Hybrid Perovskite Solar Cells by Alumina Ultrathin Films.

Over the last few years, the influence of low temperature (≤80 °C) and, in particular, of room temperature, atomic layer deposited alumina (ALD-Al2O3) on the properties of the underlying hybrid perovskites of different compositions and on the efficiency and stability of the corresponding perovskite solar cells (PSCs) is extensively investigated. The main conclusion is that most probably thanks to the presence of intrinsic defect states in the ALD-Al2O3 and in the perovskite layers, charge transfer and neutralization are possible and the entire lifetime of the PSCs is thus improved. Moreover, the migration of mobile ions between the layers is blocked by the ALD-Al2O3 layer and thus the occurrence of hysteresis in the current density-voltage characteristics of the PSCs is suppressed. Considering the uniform and nondestructive surface coverage, low thermal budget, small amount of material required, and short duration of the established ALD-Al2O3 deposition on top of hybrid perovskites, this additional, but fully solar cell technology-compatible, process step is most likely the most effective, cheapest, and fastest way to improve the efficiency and long-term stability of PSCs and thus increase their marketability.

Tuning the Magnetism in Ultrathin CrxTey Films by Lattice Dimensionality

Abstract2D magnetic crystals with atomic thickness exhibit intriguing physical properties, which have attracted considerable research interest in the related materials’ family, both in fundamental research and in developing spintronic devices. The recent discovery of some non‐van der Waals 2D magnetic crystals expands the systems. Nevertheless, the relationship between the dimensionality of microscopic magnetic exchange interactions and macroscopic magnetic properties at the 2D limit remains to be fully elucidated. Here, we have fabricated mono‐phased continuous ultrathin CrTe2 and Cr3Te4 films by molecular beam epitaxy and elucidated the diverse magnetism tuned by the dimensionality of exchange interactions by a joint study of spin‐polarized scanning tunneling microscopy, magnetization, magneto‐transport measurements, and density functional theory calculations. The transition from a zigzag‐antiferromagnetic order in the monolayer CrTe2 to a ferromagnetic (FM) order in the second‐layer CrTe2 is confirmed, which is driven by their varied in‐plane lattice constants induced change of 2D exchange interactions. A robust FM state with large perpendicular magnetic anisotropy in Cr3Te4 is observed, originating from its strong 3D exchange interactions. The observed evolution of magnetism demonstrates that the dimensionality of magnetic exchange interactions strongly influences magnetism even at the 2D limit.

Excitonic Effects on the Ultrafast Nonlinear Optical Response of MoS2 and Fluorinated Graphene/MoS2 Heterostructure Films for Photonic Applications.

In the present work, the ultrafast nonlinear optical (NLO) response of some molybdenum disulfide (MoS2), fluorinated graphene (FG), and FG/MoS2 heterostructure thin films was studied using the Z-scan and optical Kerr effect techniques employing femtosecond laser pulses at different excitation wavelengths (i.e., 400, 570, 610, 660, 800, and 1200 nm). The experiments have shown that the NLO response of the MoS2 and MoS2/FG films was significantly enhanced when the films were excited with 400, 610, and 660 nm laser pulses due to resonance effects with the close-lying excitons in these nanostructures. For a better evaluation of the resonant enhancement of the NLO response, measurements were also carried out at off-resonant wavelengths, i.e., at 570, 800, and 1200 nm. The presence of excitons in the MoS2 and MoS2/FG films resulted in strong saturable absorption and self-defocusing, with exceptionally large values of third-order susceptibilities χ(3) ranging from 10-12 to 10-13 esu. In addition, the NLO response of the MoS2/FG heterostructure was found to be stronger than that of the individual MoS2 and FG films, most probably attributed to interlayer carrier transfer. The determined NLO parameters of the studied nanostructures were found to be comparable to, and in some cases exceeded, those of other reported 2D materials known to exhibit a strong NLO response as well. These findings not only advance the fundamental understanding of the contributions of excitons on the NLO response/properties of transition metal dichalcogenide-based ultrathin films but also highlight the importance of excitons for tailoring their NLO response in view of various applications in advanced optoelectronics and photonic devices.

Evidence of Zero-Field Wigner Solids in Ultrathin Films of Cadmium Arsenide

The quantum Wigner crystal is a many-body state where Coulombic repulsion quenches the kinetic energy of electrons, causing them to crystallize into a lattice. Experimental realization of a quantum Wigner crystal at zero magnetic field has been a long-sought goal. Here, we report on the experimental evidence of a Wigner solid in ultra-thin films of cadmium arsenide (Cd3As2) at zero magnetic field. We show that a finite bias depins the domains and produces an unusually sharp-threshold current-voltage behavior. Hysteresis and voltage fluctuations point to domain motion across the pinning potential and disappear at finite temperature as thermal fluctuations overcome the potential. The application of a small magnetic field destroys the Wigner solid, pointing to an unconventional origin. We use Landau-level spectroscopy to show that the formation of the Wigner solid is closely connected to a topological transition as the film thickness is reduced. Published by the American Physical Society 2024

Superconducting fluctuations and paraconductivity in ultrathin amorphous Pb films near superconductor-insulator transitions

Superconducting fluctuations and paraconductivity in ultrathin amorphous Pb films near superconductor-insulator transitions

On the mechanism for work function change of gold electrodes by ultrathin polyethyleneimine (PEI) films: Effect of molecular order.

Polyethyleneimine (PEI) is a widely used cationic polyelectrolyte. In organic electronics, it is a universal surface modifier for shifting the electrode work function (Φ) and improving charge injection into electronic devices. This effect may depend on the conformation and dipolar order of the PEI ultrathin film, but their detailed experimental evaluation has not yet been reported. Thus, we used sum-frequency generation (SFG) spectroscopy to probe the net orientation of polar groups of PEI films on glass and gold. The films were fabricated by spin-coating from alcoholic solutions or by dip-coating from aqueous solutions of various pH values, with both branched (b-PEI) and linear (l-PEI) structures. The obtained SFG spectra and atomic force microscopy (AFM) images indicated that the conformational ordering of the PEI layers increases over the period of 14 days after fabrication, being slightly more pronounced for l-PEI vs b-PEI, and for dip-coating vs spin coating fabrication. Furthermore, both the pH of the dip-coating solutions and the substrate nature influence the final morphology and order of the adsorbed films. On glass, they are optimized at an intermediate pH 5, while on gold, the greatest homogeneity is observed at pH 2 and the largest dipolar order is observed at pH 10. The pH dependence of changes in the work function of gold by PEI (|ΔΦ|) suggests that the electronic contribution is dominant. Nevertheless, the evolution of the PEI dipolar ordering was accompanied by small variations of |ΔΦ|, suggesting that it does have a significant contribution, especially at conditions for which the electronic contribution is reduced.

Substantially Enhanced Spin Polarization in Epitaxial CrTe2 Quantum Films.

2D van der Waals (vdW) magnets, which extend to the monolayer (ML) limit, are rapidly gaining prominence in logic applications for low-power electronics. To improve the performance of spintronic devices, such as vdW magnetic tunnel junctions, a large effective spin polarization of valence electrons is highly desired. Despite its considerable significance, direct probe of spin polarization in these 2D magnets has not been extensively explored. Here, using 2D vdW ferromagnet of CrTe2 as a prototype, the spin degrees of freedom in the thin films are directly probed using Mott polarimetry. The electronic band of 50 ML CrTe2 thin film, spanning the Brillouin zone, exhibits pronounced spin-splitting with polarization peaking at 7.9% along the out-of-plane direction. Surprisingly, atomic-layer-dependent spin-resolved measurements show a significantly enhanced spin polarization in a 3 ML CrTe2 film, achieving 23.4% polarization even in the absence of an external magnetic field. The demonstrated correlation between spin polarization and film thickness highlights the pivotal influence of perpendicular magnetic anisotropy, interlayer interactions, and itinerant behavior on these properties, as corroborated by theoretical analysis. This groundbreaking experimental verification of intrinsic effective spin polarization in CrTe2 ultrathin films marks a significant advance in establishing 2D ferromagnetic atomic layers as a promising platform for innovative vdW-based spintronic devices.

Anomalously High Apparent Young's Modulus of Ultrathin Freestanding PZT Films Revealed by Machine Learning Empowered Nanoindentation.

The mechanical properties at small length scales are not only significant for understanding the intriguing size-dependent behaviors but also critical for device applications. Nanoindentation via atomic force microscopy is widely used for small-scale mechanical testing, yet determining the Young's modulus of quasi-2D films from freestanding force-displacement curve of nanoindentation remains challenging, complicated by both bending and stretching that are highly nonlinear. To overcome these difficulties, a machine learning model is developed based on the back propagation (BP) neural network and finite element training to accurately determine the Young's modulus, pretension, and thickness of freestanding films from nanoindentation force-displacement curves simultaneously, improving the computational efficiency by two orders of magnitude over conventional brute force curve fitting. Using this technique, anomalously high apparent Young's modulus is discovered of 2.8nm thick PbZr0.2Ti0.8O3 (PZT) film as large as 229.4±12.1GPa, much higher than the bulk value. The enhancement can be attributed to the strain gradient-induced flexoelectric effect, and the corresponding flexoelectric coefficient is estimated to be ≈200nCm-1. The method is developed to enable an artificial intelligence (AI) system to study the mechanical properties of a wide range of low-dimensional materials.

Free‐Standing Ultrathin Films of 2D Perovskite for Light‐Emitting Devices Operating at Strong Coupling Regime

AbstractA novel and cost‐effective method for producing free‐standing polyimide films that support a layer of 2D polycrystalline perovskite is presented. This flexible structure can be easily transferred to different substrates of various sizes and roughness, as demonstrated by depositing it on a small dielectric mirror. The experiments confirm that the presence of polyimide thin film does not affect the optical properties of the 2D perovskite, maintaining its integrity under both ambient and cryogenic conditions. Furthermore, the flexible 2D perovskite within an optical microcavity, achieving strong light‐matter coupling at room temperature is successfully embedded. The findings not only extend the frontiers of flexible optoelectronics but also emphasize its importance in improving high‐performance light‐emitting devices.

Effects of Thickness and Anisotropic Strain on Polarization Switching Properties of Sub-10nm Epitaxial Hf0.5Zr0.5O2 Thin Films

Abstract Doped HfO2-based ferroelectric (FE) films are emerging as leading contenders for next-generation FE non-volatile memories due to their excellent compatibility with complementary metal oxide semiconductor processes and robust ferroelectricity at nanoscale dimensions. Despite the considerable attention paid to the FE properties of HfO2-based films in recent years, enhancing their polarization switching speed remains a critical research challenge. We demonstrate the strong ferroelectricity of sub-10 nm Hf0.5Zr0.5O2 (HZO) thin films and show that the polarization switching speed of these thin films can be significantly affected by HZO thickness and anisotropically strained La0.67Sr0.33MO3-buffered layer. Our observations indicate that the HZO thin film thickness and anisotropically strained La0.67Sr0.33MO3 layer influence the nucleation of reverse domains by altering the phase composition of the HZO thin film, thereby reducing the polarization switching time. Although the increase in HZO thickness and anisotropic compressive strain hinder the formation of the FE phase, they can enable faster switching. Our findings suggest that FE HZO ultrathin films with polar orthorhombic structures have broad application prospects in microelectronic devices. These insights into novel methods for increasing polarization switching speed are poised to advance the development of high-performance FE devices.

Nanoscale Ga/Al substituted yttrium iron garnet films by liquid phase epitaxy

Yttrium iron garnet (YIG) has minimum damping factor and low ferromagnetic resonance (FMR) linewidth, making it a preferred material for low loss microwave and spintronic devices. The saturation magnetization of YIG is 1750 Gauss, and for low-frequency devices, a lower saturation magnetization is more suitable. Ga3+ and Al3+ are with smaller radii and non-magnetic moment, so the substitution of Ga3+ and Al3+ can decrease saturation magnetization. Here, 4.8–193.7 nm ultra-thin Y3(GaAlFe)5O12 garnet (GaAl-YIG) monocrystalline films are prepared on gadolinium gallium garnet (GGG) substrates by using the liquid-phase epitaxy (LPE) method. As expected, these films exhibit a low saturation magnetization of almost less than 100 Gauss, while their FMR linewidth remains at levels close to that of YIG. The films show a (111) orientation and in a state of tension, and the diffraction intensity of the films get stronger as films thickness increases. The free energy and density of states are calculated for different Ga/Al substitution position by density functional theory simulations. The elements show a different diffusion distance in the GaAl-YIG/GGG interface, and the variation of magnetization properties with interface width are analyzed. The surface roughness of the films is only a few angstroms. The damping factor of these ultra-thin films are on an order of 10−4 except the 4.8 nm film, which suggests that the minimum thickness of the garnet film with good performance by using the LPE method is about 10 nm. According to the analysis of structure and magnetization properties, it demonstrates that the LPE method has potential to provide nanoscale garnet films for low loss microwave and spintronic devices.

Electropolymerization of an Ultra-thin Film on bimetallic nanocomposite: enhanced performance, perfect stability for supercapacitors

Electropolymerization of an Ultra-thin Film on bimetallic nanocomposite: enhanced performance, perfect stability for supercapacitors

Toward Ultrathin: Advances in Solution-Processed Organic Semiconductor Transistors.

In recent years, organic semiconductor (OSC) ultrathin films and their solution-processed organic field-effect transistors (OFETs) have garnered attention for their high flexibility, light weight, solution processability, and tunable optoelectronic properties. These features make them promising candidates for next-generation optoelectronic applications. An ultrathin film typically refers to a film thickness of less than 10 nm, i.e., several molecular layers, which poses challenges for OSC materials and solution-processed methods. In this paper, first we introduce the carrier-transport regulation mechanism under ultrathin limits. Second, we summarize various solution-processed techniques for OSC ultrathin films and elucidate advances in their OFETs performance, such as enhanced or maintained mobilities, improved switching ratios, reduced threshold voltages, and minimized contact resistance. The relationship between the ultrathin-film thickness, microstructure of various OSCs (small molecules and polymers), and device performance is discussed. Third, we explore the recent application of OSC ultrathin-film-based OFETs, such as gas sensors, biosensors, photodetectors, and ferroelectric OFETs (Fe-OFETs). Finally, the conclusion is drawn, and the challenges and prospects of ultrathin OSC transistors are presented. Nowadays, research on ultrathin films is still in its early stages; further experience in precise film deposition control is crucial to advancing research and broadening the scope of applications for OSC ultrathin devices.

Growth and Structure of Ultrathin Iron Silicate and Iron Germanate Films

Growth and Structure of Ultrathin Iron Silicate and Iron Germanate Films

Electrochemically-Switched Microwave Response of MXene in Organic Electrolyte.

The increasingly complex electromagnetic (EM) environment necessitates advanced electrically controllable electromagnetic interference (EMI) shielding materials that can adapt to varying EM conditions. This study develops a flexible electrochemically tunable EMI shielding device based on ultrathin Ti3C2Tx MXene films, exhibiting reversible shielding effectiveness (SE) modulation from 18.9 to 26.2dB in X band at 0.1 and -1.5V. Unlike the previously reported mechanism relying on interlayer spacing adjustments, the work leverages transformations of charging state and surface chemistry for tunability during the electrochemical process. The Ti3C2Tx flake size is also evidenced to play a crucial role, with smaller flakes offering higher absorption modulation despite lower SE modulation, enabling the device with high designability. When integrated with Salisbury screen structure, the device achieves adjustable absorption from 93.560% at 0.1V to 99.996% at -1V, showing a tunable reflection suppression ratio up to 32dB with an effective bandwidth of 4.2GHz. Additionally, incorporating resonant cavity structure enables absorption-dominated (over 90%) microwave-responsive switching at 0.1 and -1.5V. This work highlights significant potential of adaptive EMI shielding materials for applications in smart electronic protection, EM switch, and radar camouflage.

Synthesis of Ultrathin Film PEGDMA Hydrogels Coated onto Different Surfaces by Atmospheric Pressure Plasma: Characterization and Potential Features for the Biomedical Field

AbstractThe preparation of resistant ultrathin film (utf) hydrogels coated onto different working surfaces (e.g., fabrics) is paying increasing attention as an advantageous strategy for customizing their resultant properties. More specifically, poly(ethylene glycol) (PEG)‐based utf‐hydrogels are relevant for their superior biocompatibility or antibiofouling properties. However, promoting the generation of poly(ethylene glycol) dimethacrylate (PEGDMA) cross‐links ideally without the use of initiators or other cross‐link agents, which might compromise the final bioactivity of the system, is complicated. Moreover, the actual synthesis techniques used for the preparation of such utf‐hydrogels face important drawbacks like high scale‐up costs or important geometrical restrictions, completely hindering its technological transfer. Herein, for the first time and easy and technologically scalable technology is reported for the synthesis and direct deposition of PEGDMA400 utf‐hydrogels onto different substrates based on atmospheric pressure nanosecond pulsed plasma approach. The advantages of the technology are explored and discussed, reporting the ready‐to‐use transparent coating of fabrics. After washing the samples using washing programs of a commercial laundry machine, coatings are still well adhered, showing excellent stability. Finally, the resultant properties of PEGDMA400 utf‐hydrogels are exhaustively characterized using in operando conditions in order to elucidate their potential capabilities in the biomedical field.

Enhancing Stability in All-Vacuum-Evaporated Hybrid Perovskite Solar Cells via a Bipolar Host as a Hole-Transporting Layer.

Growing an ultrathin hybrid organic-inorganic perovskite film while maintaining high efficiency and addressing photostability challenges for commercial devices remains a significant hurdle. In this study, we explore the incorporation of organometallic copper phthalocyanine (CuPc) and MS-OC (a previously published spiro-based interfacial material for perovskite solar cells (PSCs), featuring an ortho-oriented carbazole donor) as an addition to the hole-transporting layer (HTL) in all-vacuum-deposited Cs0.06FA0.94Pb(I0.68Br0.32)3 PSCs. By innovatively introducing a 3 nm-thin MS-OC layer at the CuPc-perovskite interface, we achieve a deeper understanding of the crystallographic dynamics of perovskites, resulting in a uniform and pinhole-free film. We demonstrate that PSCs utilizing the CuPc HTL with an MS-OC interfacial layer in a p-i-n architecture achieve a power conversion efficiency (PCE) of up to 14.42%. Remarkably, the CuPc/MS-OC-based device exhibits outstanding long-term photostability, maintaining its initial PCE over 400 h (T100 = 400 h) under continuous sunlight illumination. By configuring the device architecture as ITO/MoO3/CuPc/MS-OC/perovskite/C60/BCP/Ag, we find that the evaporated MS-OC thin films effectively reduce nonradiative losses, passivate the perovskite, and enhance device performance. Our findings indicate that the polarity of the underlying surface significantly influences perovskite nucleation, underscoring the potential to improve photostability by controlling interfacial imperfections.

Atomic scale in-situ observation of gas-solid interaction regulating the pre-nucleation process of Pd atomic clusters

Advancements in nanotechnology have propelled the understanding of atomic-scale nucleation processes, essential for the evolution of atomic manufacturing. The process of amorphous precursors nucleation showcases a complex transition influenced by various factors. Utilizing aberration-corrected ETEM and theoretical calculation, we explore the nucleation of amorphous Pd atomic clusters. This study examines the nucleation dynamics and gas-solid interaction regulating of Pd clusters on ultrathin carbon films, prepared via electron beam evaporation. HRTEM observation and FFT analysis reveal that, in the early stage of nucleation, Pd cluster growth predominantly follows an Ostwald ripening-like mechanism. Atoms from smaller clusters migrate and attach to larger ones, facilitating their progression to critical nucleation size. Environmental conditions significantly influence this process; hydrogen atmospheres lower the surface energy of Pd clusters, reducing the critical nucleation size, while argon atmospheres impede growth of Pd clusters by occupying migration sites on the carbon surface. These insights into atomic cluster behavior and environmental interactions are crucial for understanding the early stages of nucleation from amorphous to crystalline and can help opens new avenues for the controlled fabrication of materials with optimized functionalities.