Atomic layer deposition assisted fabrication of large-scale metal nanogaps for surface enhanced Raman scattering.

Metal nanogaps can confine electromagnetic field into extremely small volumes, exhibiting strong surface plasmon resonance effect. Therefore, metal nanogaps show great prospects in enhancing light-matter interaction. However, it is still challenging to fabricate large-scale (centimeter scale) nanogaps with precise control of gap size at nanoscale, limiting the practical applications of metal nanogaps. In this work, we proposed a facile and economic strategy to fabricate large-scale sub-10 nm Ag nanogaps by the combination of atomic layer deposition (ALD) and mechanical rolling. The plasmonic nanogaps can be formed in the compacted Ag film by the sacrificial Al2O3deposited via ALD. The size of nanogaps are determined by the twice thickness of Al2O3with nanometric control. Raman results show that SERS activity depends closely on the nanogap size, and 4 nm Ag nanogaps exhibit the best SERS activity. By combining with other porous metal substrates, various sub-10 nm metal nanogaps can be fabricated over large scale. Therefore, this strategy will have significant implications for the preparation of nanogaps and enhanced spectroscopy.

Editorial for focus on manipulations of atomic and molecular layers and its applications in energy, environment sciences and optoelectronic devices.

This Focus aims at showcasing the significance of manipulating atomic and molecular layers for various applications. To this end, this Focus collects 15 original research papers featuring the applications of atomic layer deposition, chemical vapor deposition, wet chemistry, and some other methods for manipulations of atomic and molecular layers in lithium-ion batteries, supercapacitors, catalysis, field-effect transistors, optoelectronics, and others.

Reaction mechanism of nickel sulfide atomic layer deposition using bis(N,N'-di-tert-butylacetamidinato)nickel(II) and hydrogen sulfide.

As a unique nanofabrication technology, atomic layer deposition (ALD) has been used in the microelectronics, catalysis, environmental and energy fields. As an energy and catalytic material, nickel sulfide has excellent electrochemical and catalytic activities and has attracted extensive attention. In this work, the reaction mechanism for nickel sulfide ALD from an amidine metal precursor was investigated using density functional theory (DFT) calculations. The results show that the first amidine ligand of bis(N,N'-di-tert-butylacetamidinato)nickel(II) [Ni(tBu-MeAMD)2] can be easily eliminated on the sulfhydrylated surface. The second amidine ligand can also react with the adjacent sulfhydryl group to generate the N,N'-di-tert-butylacetamidine (tBu-MeAMD-H) molecule, which can strongly interact with the Ni atom on the surface and be difficult to be desorbed. In the subsequent H2S reaction, the tBu-MeAMD-H molecule can be exchanged with the H2S precursor. Ultimately, the tBu-MeAMD-H molecule can be desorbed and H2S can be dissociated to form two sulfhydrylated groups on the surface. Meanwhile, the -SH of a H2S molecule can be exchanged with the second tBu-MeAMD ligand. These insights into the reaction mechanism of nickel sulfide ALD can provide theoretical guidance to design the metal amidinate precursors and improve the ALD process for metal sulfides.

In Situ Formation of Polycyclic Aromatic Hydrocarbons as an Artificial Hybrid Layer for Lithium Metal Anodes.

Nonuniform Li deposition causes dendrites and low Coulombic efficiency (CE), seriously hindering the practical applications of Li metal. Herein, we developed an artificial solid-state interphase (SEI) with planar polycyclic aromatic hydrocarbons (PAHs) on the surface of Li metal anodes by a facile in situ formation technology. The resultant dihydroxyviolanthron (DHV) layers serve as the protective layer to stabilize the SEI. In addition, the oxygen-containing functional groups in the soft and conformal SEI film can regulate the diffusion and transport of Li ions to homogenize the deposition of Li metal. The artificial SEI significantly improves the CEs and shows superior cyclability of over 1000 h at 4 mAh cm-2. The LiFePO4/Li cell (2.8 mAh cm-2) enables a long cyclability for 300 cycles and high CEs of 99.8%. This work offers a new strategy to inhibit Li dendrite growth and enlightens the design on stable SEI for metal anodes.

Alterations in the gut microbiota and metabolite profiles of thyroid carcinoma patients.

The aim of our study was to investigate the relationship among the gut microbiota community, metabolite profiles and thyroid carcinoma (TC). First, 30 TC patients and 35 healthy controls (HCs) fecal samples were applied to characterize the gut microbial community using 16S rRNA gene sequencing. Differential microbiota compositions were observed, with significant enrichment of 19 and depletion of 8 genera in TC samples compared to those in HCs (Q value <0.05), and some genera were correlated with various clinical parameters, such as lipoprotein A and apolipoprotein B. Furthermore, 6 different genera distinguished TC patients from HCs with the AUC of 0.94. The PICRUSt analysis showed 12 remarkably different metabolic pathways (Q value <0.05). Subsequently, we systematically analyzed the gut microbiota and metabolites in the same TC patients (n = 15) and HCs (n = 15). The characteristics of the gut microbiota community were mostly consistent with the above results (30 TC patients and 35 HCs), and liquid chromatography mass spectrometry analysis was performed to characterize the metabolite profiles. In total, 21 different genera (Q value <0.05) and 72 significantly changed metabolites (VIP > 1.0 and p < 0.05) were observed and correlated to each other. Eight metabolites combined with 5 genera were more effective in distinguishing TC patients from HCs (AUC = 0.97). In conclusion, our study presents a comprehensive landscape of the gut microbiota and metabolites in TC patients, and provides a research direction of the mechanism of interaction between gut microbiota alteration and TC pathogenesis.

Growth Mechanism, Ambient Stability, and Charge Trapping Ability of Ti-Based Maleic Acid Hybrid Films by Molecular Layer Deposition.

Ti-based maleic acid (MA) hybrid films were successfully fabricated by molecular layer deposition (MLD) using organic precursor MA and inorganic precursor TiCl4. The effect of deposition temperature on the growth rate, composition, and bonding mode of hybrid thin films has been investigated systematically. With increasing temperature from 140 to 280 °C, the growth rate decreases from 1.42 to 0.16 Å per MLD cycle with basically unchanged composition ratio of C:O:Ti in the films. Fourier transform infrared spectra indicate that all hybrid films show preference for bidentate bonding mode. Further analyses of X-ray photoelectron spectroscopy and in situ quartz crystal microbalance elucidate that as-deposited MLD Ti-MA hybrid films consist of inorganic Ti-O-Ti units and organic-inorganic Ti-MA units. In addition, the density functional theory calculation was performed to investigate the possible reaction mechanism of the TiCl4-MA MLD process, which is well consistent with experimental results. More importantly, upon comparison with the TiCl4-fumaric acid MLD system, it is demonstrated that the cis- and trans-configurations of butenedioic acid influence the MLD growth, bonding mode, stability, and charging ability of MLD hybrid films. Ti-MA hybrid films exhibit better stability and charging ability than Ti-FA hybrid films, benefiting from the inorganic Ti-O-Ti units in the hybrid films.

Interfacial catalysis in and initial reaction mechanism of Al2O3 films fabricated by atomic layer deposition using non-hydrolytic sol-gel chemistry.

Atomic layer deposition (ALD) is a powerful nanofabrication technique that can precisely control the composition, structure, and thickness of thin films at the atomic scale, and is widely used in the fields of electronic displays, microelectronics, catalysis, coatings, and energy storage and conversion. ALD of metal oxide thin films can be completed using metal alkoxides as the oxygen source, which is similar to the non-hydrolytic sol-gel (NHSG) technique. Density functional theory calculations show that metal alkoxides, such as Al(OiPr)3 and Al(OEt)3, can directly form M-O bonds through strong chemisorption on the surface. Meanwhile, alkyl groups can be eliminated through the formation of alkyl halides and alkenes, which can be catalyzed by interfacial interactions between alkyl groups and the surface. Such noncovalent catalysis resulting from interfacial interaction can be termed as interfacial catalysis. This can be characterized by the difference between the interfacial interaction energies of the transition state and the corresponding intermediate based on natural bond analysis. We expect that such interfacial catalysis can be used in precursor designs, improvement of ALD of oxides and as a new characterization method for other interfacial catalysis and noncovalent catalysis processes.

A comprehensive analysis of candidate genes and pathways in pancreatic cancer.

The study aimed to dissect the molecular mechanism of pancreatic cancer by a range of bioinformatics approaches. Three microarray datasets (GSE32676, GSE21654, and GSE14245) were downloaded from Gene Expression Omnibus database. Differentially expressed genes (DEGs) with logarithm of fold change (|logFC|) >0.585 and p value <0.05 were identified between pancreatic cancer samples and normal controls. Transcription factors (TFs) were selected from the DEGs based on TRASFAC database. Gene ontology and Kyoto Encyclopedia of Genes and Genomes pathway enrichment analyses were performed for the DEGs using The Database for Annotation, Visualization and Integrated Discovery (p value <0.05), followed by construction of protein-protein interaction (PPI) network using Search Tool for the Retrieval of Interacting Genes software. Latent pathway identification analysis was applied to analyze the DEGs-related pathways crosstalk and the pathways with high weight value were included in the pathway crosstalk network using Cytoscape. Sixty-five DEGs were screened out. CCAAT/enhancer-binding protein delta (CEBPD), FBJ osteosarcoma oncogene B (FOSB), Stratifin (SFN), Krüppel-like factor 5 (KLF5), Pentraxin 3 (PTX3), and nuclear receptor subfamily 4, group A, member 3 (NR4A3) were important TFs. Interleukin-6 (IL-6) was the hub node of the PPI network. DEGs were significantly enriched in NOD-like receptor signaling pathway which was primarily interacted with inflammation and immune related pathways (cytosolic DNA-sensing, hematopoietic cell lineage, intestinal immune network for IgA production and chemokine pathways). The study suggested CEBPD, FOSB, SFN, KLF5, PTX3, NR4A3, IL-6, and NOD-like receptor pathways were involved in pancreatic cancer.

Atomic layer deposition of Co3O4 on carbon nanotubes/carbon cloth for high-capacitance and ultrastable supercapacitor electrode.

Co3O4 nanolayers have been successfully deposited on a flexible carbon nanotubes/carbon cloth (CC) substrate by atomic layer deposition. Much improved capacitance and ultra-long cycling life are achieved when the CNTs@Co3O4/CC is tested as a supercapacitor electrode. The improvement can be from the mechanically robust CC/CNTs substrate, the uniform coated high capacitance materials of Co3O4 nanoparticles, and the unique hierarchical structure. The flexible electrode of CNTs@Co3O4/CC with high areal capacitance and excellent cycling ability promises great potential for developing high-performance flexible supercapacitors.

Photocatalytic activity and photocorrosion of atomic layer deposited ZnO ultrathin films for the degradation of methylene blue.

ZnO ultrathin films with varied thicknesses of 7-70 nm were prepared at 200 °C on Si and fused quartz substrates by atomic layer deposition (ALD). The impact of film thickness and annealing temperature on the crystallinity, morphology, optical bandgap, and photocatalytic properties of ZnO in the degradation of methylene blue (MB) dye under UV light irradiation (λ = 365 nm) has been investigated deeply. The as-deposited 28 nm thick ZnO ultrathin film exhibits highest photocatalytic activity, ascribed to the smallest band gap of 3.21 eV and proper thickness. The photocorrosion effect of ALD ZnO ultrathin films during photocatalytic process is observed. The presence of MB significantly accelerates the dissolution of ZnO ultrathin films. The possible photoetching mechanism of ZnO in MB solution is proposed.

Ferroelectric-field-effect-enhanced electroresistance in metal/ferroelectric/semiconductor tunnel junctions.

Ferroelectric tunnel junctions (FTJs), composed of two metal electrodes separated by an ultrathin ferroelectric barrier, have attracted much attention as promising candidates for non-volatile resistive memories. Theoretical and experimental works have revealed that the tunnelling resistance switching in FTJs originates mainly from a ferroelectric modulation on the barrier height. However, in these devices, modulation on the barrier width is very limited, although the tunnelling transmittance depends on it exponentially as well. Here we propose a novel tunnelling heterostructure by replacing one of the metal electrodes in a normal FTJ with a heavily doped semiconductor. In these metal/ferroelectric/semiconductor FTJs, not only the height but also the width of the barrier can be electrically modulated as a result of a ferroelectric field effect, leading to a greatly enhanced tunnelling electroresistance. This idea is implemented in Pt/BaTiO3/Nb:SrTiO3 heterostructures, in which an ON/OFF conductance ratio above 10(4), about one to two orders greater than those reported in normal FTJs, can be achieved at room temperature. The giant tunnelling electroresistance, reliable switching reproducibility and long data retention observed in these metal/ferroelectric/semiconductor FTJs suggest their great potential in non-destructive readout non-volatile memories.

A satisfaction survey of current medicines used for migraine therapy in China: is Chinese patent medicine effective compared with Western medicine for the acute treatment of migraine?

OBJECTIVE: To investigate the patient satisfaction with medications commonly used for migraine therapy in patients seen in headache clinic in China with emphasis on the evaluation of Chinese patent medicine (CPM) in relieving acute migraine attack. METHODS: Patients admitted at headache clinics in the neurological departments of four hospitals during April to October 2011 were enrolled in the investigation. The questionnaire was designed based on the validation of a diagnostic questionnaire for a population-based survey in China in 2009. RESULTS: Among 219 eligible patients, 58% had used CPM at the acute attack of migraine while the guideline-recommended treatments were seldom used. However, patients using CPMs were less satisfied than those using Western Medicines (WMs) in either single medication groups or mixed medication groups (P < 0.05). CONCLUSION: Fifty-eight percent of the eligible respondents in Guangdong and Guangxi Province had used CPM at the acute attack of migraine, but based on our data, the effect of CPM on treating migraine attack was poor with low satisfaction compared with WMs. However, many factors may bias or explain our findings. This suggests the need for accelerated research in understanding patient choice, treatment availability, and use of medications.

Reinforcement Effects on Tensile Behavior of Ultra-High-Performance Concrete (UHPC) with Low Steel Fiber Volume Fractions.

Ultra-high-performance concrete (UHPC) with a low steel fiber volume fraction offers lower material costs than UHPC with typical steel fiber volume fractions, and has the potential to mitigate the ductility degradation of rebar-reinforced UHPC (R-UHPC). This study explores the reinforcement effect on the tensile behavior of UHPC with a low fiber volume fraction with the aim of facilitating more cost-efficient UHPC applications. The axial tensile behavior of 30 UHPC specimens with low fiber volume fractions at different reinforcement ratios was tested through direct tensile tests. The findings indicate that adopting UHPC with a low fiber volume fraction can significantly mitigate the ductility deterioration of rebar-reinforced UHPC (R-UHPC), and both increasing the reinforcement ratio and decreasing the fiber volume fraction contribute to the improvement in ductility. The failure modes of R-UHPC are determined by the ratio of reinforcement ratio and fiber volume fraction, rather than a single parameter, which also means that R-UHPC with different parameters may correspond to different methods to predict tensile load-bearing capacity. For UHPC with a fiber volume fraction low to 0.5%, incorporating steel rebars gives superior multi-crack cracking behavior and excellent capacity to restrict the maximum crack width. Increasing the fiber volume fraction from 0.5% to 1.0% at the same reinforcement ratio will yield little benefit other than an increase in tensile load-bearing capacity.

[Relationship of alcohol drinking and tea consumption with the risk of nasopharynx cancer among Chinese population: a meta-analysis].

OBJECTIVE: To evaluate the relationship and strength of association for alcohol drinking and tea consumption with the riskS of nasopharynx cancer among Chinese population so as to provide control rationales for nasopharynx cancer in China. METHODS: A systematic search of 3 Chinese electronic databases (CNKI, VIP, Wanfang) and 3 English databases (Pubmed, ScienceDirect and SpringerLink) up to March 2013 was performed. Two reviewers independently conducted the literature search, examined eligibility and performed data extraction and quality evaluations. Pooled odd ratio (OR) value and 95%CI value were calculated with random-effects model weighted with inverse of variances. RESULTS: A total of 14 studies (including 3 cohort and 11 case-control) involving 6559 cases of nasopharynx cancer and 10 567 controls from 6 provinces were included. The pooled OR between alcohol drinking and risks of nasopharynx cancer was 1.12 (95%CI: 0.98-1.26; I(2) = 44.5%, P = 0.037). Compared with the non-drinkers, the risks of nasopharynx cancer for regular drinkers and occasional drinkers were 1.18 (95%CI: 1.00-1.38; I(2) = 0.0%, P = 0.578) and 0.76 (95%CI: 0.65-0.89; I(2) = 33.4%, P = 0.212). And the association of tea consumption with the risks of nasopharynx cancer was 0.53 (95%CI: 0.43-0.60; I(2) = 17.9%, P = 0.301). CONCLUSIONS: In China, occasional alcohol drinking may decrease the risks of nasopharynx cancer while regular drinking elevates the risks. And there is significantly protective effect for tea consumption on the risks of nasopharynx cancer.

Atomic/Molecular Layer-Deposited Laminated Li2O-Lithicone Interfaces Enabling High-Performance Silicon Anodes.

Silicon-based materials are of long-standing interest as the anodes for next-generation lithium-ion batteries, yet their low initial Coulombic efficiency and poor interfacial stability are lethal limitations. In this work, we used atomic layer deposition (ALD) and molecular layer deposition (MLD) techniques to fabricate a lithium-containing laminated Li2O-lithicone hybrid film (∼5 nm) on a silicon electrode. The laminated film provides an additional surface Li source around silicon cores, which can partially reimburse the Li loss during battery cycling. Characterization of interfacial components shows that such a laminated Li2O-lithicone interface undergoes gentle element changes and participates in a hybrid solid electrolyte interphase with Li2CO3, Li2O, LixPOFy, and LiF species. Finite element model analysis and morphology characterization demonstrate that the laminated structure design can help relieve the interfacial stress and thus retain the integrity and reactivity of the silicon composite anode during cycling. Moreover, the lithium-based laminated film leads to a fast Li+ migration kinetics on the surface of the electrode as revealed by the galvanostatic intermittent titration technique and density functional theory calculation. Benefiting from the above merits, a silicon anode with a 91.2% initial Coulombic efficiency, a rate performance of 1460 mA h g-1 at 2 A g-1, and a reversible capacity over 646 mA h g-1 after 850 cycles was achieved. This work exemplifies the advantages of lithium-based hybrid films precisely engineered by ALD/MLD techniques for improving performances of advanced silicon anode batteries and deepens understandings on the mechanism of interfacial stability and reaction kinetics.

Unraveling the connection between gut microbiota and Alzheimer's disease: a two-sample Mendelian randomization analysis.

Purpose: Studies have shown a close relationship between gut microbiota (GM) and Alzheimer's disease (AD). However, the causal relationship between them remains unclear. Methods: We conducted a genome-wide association study (GWAS) using publicly available summary statistics data for GM and AD. We extracted independent genetic loci significantly associated with GM relative abundances as instrumental variables based on predefined thresholds (p < 1*e-5). The inverse variance-weighted (IVW) method was primarily used for causal relationship assessment. Additional analyses, including MR-Egger, weighted median, simple mode, and weighted mode, were performed as supplementary analyses. Results: IVW analysis revealed significant correlations between certain microbial taxa and the risk of AD. Higher abundances of Actinobacteria at the class level, phylum. Actinobacteria, class. Deltaproteobacteria, order. Desulfovibrionales, genus. Oscillospira, and genus. Ruminococcaceae UCG004 (p < 0.048) was found to be positively associated with an elevated risk of AD. However, within the genus-level taxa, Ruminococcus1 (p = 0.030) demonstrated a protective effect on lowering the risk of AD. In addition, to ensure the robustness of the findings, we employed Cochrane's Q test and leave-one-out analysis for quality assessment, while the stability and reliability of the results were validated through MR-Egger intercept test, MR-PRESSO global test, and sensitivity analysis. Conclusion: This study provided a comprehensive analysis of the causal relationship between 211 GM taxa and AD. It discerned distinct GM taxa linked to the susceptibility of AD, thereby providing novel perspectives on the genetic mechanisms governing AD via the GM. Additionally, these discoveries held promise as valuable biomarkers, enabling the identification of potential therapeutic targets and guiding forthcoming AD investigations.

Electrochemical Resistive Switching in Nanoporous Hybrid Films by One-Step Molecular Layer Deposition.

An organic-inorganic hybrid resistive random-access memory based on a nanoporous zinc-based hydroquinone (Zn-HQ) thin film has been constructed with a Pt/Zn-HQ/Ag sandwich structure. The porous Zn-HQ functional layer was directly fabricated by a one-step molecular layer deposition. These Pt/Zn-HQ/Ag devices show a typical electroforming-free bipolar resistive switching characteristic with lower operation voltages and higher on/off ratio above 102. Our nanoporous hybrid devices can also realize multilevel storage capability and exhibit excellent endurance/retention properties. The connection and disconnection of Ag conductive filaments in nanoporous Zn-HQ thin film follow the electrochemical metallization mechanism. Our computational simulations confirm that the existence of nanopores in Zn-HQ thin films facilitates the Ag filament formation, contributing to the high performance of our hybrid devices.

Atomic layer deposition assisted non-destructive strategy for cleaning Ag dendrites based SERS substrates.

Ag dendrites have recently been widely reported due to their excellent surface-enhanced Raman scattering (SERS) properties. However, prepared pristine Ag dendrites are usually contaminated by organic impurities, which has a huge negative impact on their Raman detection and greatly limits their practical applications. In this paper, we reported a facile strategy to obtain clean Ag dendrites by high temperature decomposition of organic impurities. With the assistance of ultra-thin coating via atomic layer deposition (ALD), the nanostructure of Ag dendrites can be retained at high temperature. SERS activity can be recovered after etching ALD coating. Chemical composition tests indicate that the organic impurities can be effectively removed. As a result, the clean Ag dendrites can obtain more clearly discernible Raman peaks and lower limits of detection than the pristine Ag dendrites. Furthermore, it was demonstrated that this strategy is also applicable to clean other substrates, such as gold nanoparticles. Therefore, high temperature annealing with the help of ALD sacrifice coating is a promising and non-destructive strategy to clean the SERS substrates.

Structure-evolution-designed amorphous oxides for dielectric energy storage.

Recently, rapidly increased demands of integration and miniaturization continuously challenge energy densities of dielectric capacitors. New materials with high recoverable energy storage densities become highly desirable. Here, by structure evolution between fluorite HfO2 and perovskite hafnate, we create an amorphous hafnium-based oxide that exhibits the energy density of ~155 J/cm3 with an efficiency of 87%, which is state-of-the-art in emergingly capacitive energy-storage materials. The amorphous structure is owing to oxygen instability in between the two energetically-favorable crystalline forms, in which not only the long-range periodicities of fluorite and perovskite are collapsed but also more than one symmetry, i.e., the monoclinic and orthorhombic, coexist in short range, giving rise to a strong structure disordering. As a result, the carrier avalanche is impeded and an ultrahigh breakdown strength up to 12 MV/cm is achieved, which, accompanying with a large permittivity, remarkably enhances the energy storage density. Our study provides a new and widely applicable platform for designing high-performance dielectric energy storage with the strategy exploring the boundary among different categories of materials.

Growth behavior of Ir metal formed by atomic layer deposition in the nanopores of anodic aluminum oxide.

The conformal coating or surface modification in high aspect ratio nanostructures is a tough challenge using traditional physical/chemical vapor deposition, especially for metal deposition. In this work, the growth behavior of iridium (Ir) metal formed by atomic layer deposition (ALD) in anodic aluminum oxide (AAO) templates was explored deeply. It is found that the surface hydrophilicity is crucial for the nucleation of ALD Ir. An in situ ALD Al2O3 layer with an ultra-hydrophilic surface can greatly promote the nucleation of ALD Ir in AAO nanopores. The effect of the Ir precursor pulse time, diameter, and length of AAO nanopores on the infiltration depth of ALD Ir was investigated systematically. The results show that the infiltration depth of ALD Ir in AAO nanopores is in proportion to the pore diameter and the square root of the Ir precursor pulse time, which follows a diffusion-limited model. Furthermore, the Ir precursor pulse time to obtain conformal Ir coating throughout all the AAO channels is in proportion to the square of the aspect ratio of AAO templates. In addition, the conformal Ir deposition in AAO nanopores is also related to the Ir precursor purge time and the O2 partial pressure. Insufficient Ir purge time could cause a CVD-like reaction, leading to the reduction of the infiltration depth in AAO. Higher O2 partial pressure can facilitate Ir nucleation with more Ir precursor consumption at the entrance of nanopores, decreasing the infiltration depth in AAO nanopores, so appropriate O2 partial pressure should be chosen for ALD Ir in high aspect ratio materials. Above all, our research is valuable for surface modification or coating of metal by ALD in high aspect ratio nanostructures for 3D microelectronics, nano-fabrication, catalysis and energy fields.