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Distinguishing Zigzag and Armchair Edges on Graphene Nanoribbons by X-ray Photoelectron and Raman Spectroscopies
摘要： Graphene nanoribbons (GNRs) have recently emerged as alternative 2D semiconductors owing to their fascinating electronic properties that include tunable band gaps and high charge-carrier mobilities. Identifying the atomic-scale edge structures of GNRs through structural investigations is very important to fully understand the electronic properties of these materials. Herein, we report an atomic-scale analysis of GNRs using simulated X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Tetracene with zigzag edges and chrysene with armchair edges were selected as initial model structures, and their XPS and Raman spectra were analyzed. Structurally expanded nanoribbons based on tetracene and chrysene, in which zigzag and armchair edges were combined in various ratios, were then simulated. The edge structures of chain-shaped nanoribbons composed only of either zigzag edges or armchair edges were distinguishable by XPS and Raman spectroscopy, depending on the edge type. It was also possible to distinguish planar nanoribbons consisting of both zigzag and armchair edges with zigzag/armchair ratios of 4:1 or 1:4, indicating that it is possible to analyze normally synthesized GNRs because their zigzag to armchair edge ratios are usually greater than 4 or less than 0.25. Our study on the precise identification of GNR edge structures by XPS and Raman spectroscopy provides the groundwork for the analysis of GNRs.
关键词： X-ray photoelectron spectroscopy,Graphene nanoribbons,armchair edges,zigzag edges,Raman spectroscopy
更新于2025-09-04 15:30:14
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Thermal atomic layer deposition of Sn metal using SnCl <sub/>4</sub> and a vapor phase silyl dihydropyrazine reducing agent
摘要： This work explores a novel, thermal atomic layer deposition (ALD) process to deposit tin metal at a low temperature. The authors employ 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (DHP) to reduce SnCl4 on silicon substrates. The authors explored a range of temperatures between 130 and 210 °C to determine the ALD window, which was found to be 170–210 °C. The authors show that this process yields a growth rate of ～0.3 ? per cycle at 190 °C. Furthermore, X-ray photoelectron spectroscopy results showed that the ?lm impurities are reduced for depositions within the ALD window. The reaction mechanism was explored using in situ mass spectrometry and in situ quartz crystal microbalance (QCM). Within the ALD temperature window, the QCM results showed a saturated mass gain during the SnCl4 exposure and a net mass loss during the DHP dose. Consistent with the QCM results, in situ mass spectroscopy data indicate that the DHP exposure step removes surface Cl via formation of volatile trimethylsilyl chloride and pyrazine by-products, effectively reducing the oxidation state of surface-bound Sn. This work is the ?rst thermal Sn metal ALD process to be reported in literature and the oxidation/reduction chemistry presented here may be applied to other metal precursors, increasing the applicability of metal ALD use in industry.
关键词： quartz crystal microbalance,X-ray photoelectron spectroscopy,ALD window,SnCl4,mass spectrometry,tin metal,thermal atomic layer deposition,DHP
更新于2025-09-04 15:30:14
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In-doped As2Se3 thin films studied by Raman and X-ray photoelectron spectroscopies
摘要： Amorphous In-doped As2Se3 films with nominal indium contents x up to 7 at. % were prepared by thermal evaporation. Atomic force microscopy studies confirm the uniform film structure with a surface roughness near 5 nm, noticeably higher than for similarly prepared undoped As2Se3 film. X-ray photoelectron spectroscopy (XPS) studies enabled the chemical composition of the films to be examined. As follows from the XPS data, the In content in the film strongly decreases with the film depth. For films with x ≥ 2 at.%, Raman features attributed to transverse and longitudinal optical phonons of InAs are revealed in the Raman spectra as an evidence for the formation of InAs nanocrystallites in the As2Se3:In film under laser illumination.
关键词： X-ray photoelectron spectroscopy,amorphous,film,Raman scattering,atomic force microscopy,semiconductor nanocrystals
更新于2025-09-04 15:30:14
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Electronic structure of the polymer-cathode interface of an organic electroluminescent device investigated using operando hard x-ray photoelectron spectroscopy
摘要： The electronic structure of a polymer-cathode interface of an operating organic light-emitting diode (OLED) was directly investigated using hard X-ray photoelectron spectroscopy (HAXPES). The potential distribution pro?le of the light-emitting copolymer layer as a function of the depth under the Al/Ba cathode layer in the OLED depended on the bias voltage. We found that band bending occurred in the copolymer of 9,9-dioctyl?uorene (50%) and N-(4-(2-butyl)-phenyl)diphenylamine (F8-PFB) layer near the cathode at 0 V bias, while a linear potential distribution formed in the F8-PFB when a bias voltage was applied to the OLED. Direct observation of the built-in potential and that band bending formed in the F8-PFB layer in the operating OLED suggested that charges moved in the F8-PFB layer before electron injection from the cathode.
关键词： polymer-cathode interface,band bending,organic light-emitting diode,electronic structure,hard X-ray photoelectron spectroscopy
更新于2025-09-04 15:30:14
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XPS investigation of F-doped MnO <sub/>2</sub> nanosystems fabricated by plasma assisted-CVD
摘要： Supported Mn(IV) oxide nanomaterials were prepared by plasma assisted-chemical vapor deposition from Ar/O2 plasmas starting from a fluorinated Mn(II) β-diketonate diamine adduct. Under the adopted conditions, the target compound served as a single-source molecular precursor for the obtainment of MnO2 nanosystems uniformly doped with fluorine. The overall F content in the target materials, composed of phase-pure β-MnO2, could be tailored as a function of the deposition temperature from 100 to 400 °C, a result of particular importance in view of photocatalytic and gas sensing applications. In the present study, attention is specifically devoted to the investigation of a representative specimen by means of x-ray photoelectron spectroscopy. Besides the wide scan spectrum, a detailed analysis of C 1s, O 1s, Mn 2p, Mn 3s, and F 1s photoelectron peaks is presented and discussed. The analyses reveal the formation of MnO2 free from other manganese oxides, with fluorine present in different chemical states, i.e., lattice F plus traces of precursor residuals at the system surface.
关键词： fluorine doping,x-ray photoelectron spectroscopy,PA-CVD,manganese oxide
更新于2025-09-04 15:30:14
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Atomic layer etching of chrome using ion beams
摘要： In this study, two Cr atomic layer etching (ALE) methods have been applied for the precise control of Cr etching. The first one involves O radical adsorption followed by Cl+ ion desorption (ALE with chemical ion desorption; chemical anisotropic ALE), and the second one involves Cl/O radical adsorption followed by Ar+ ion desorption (ALE with physical ion desorption; physical anisotropic ALE). Their effects on Cr etch characteristics were also investigated. For both the ALE methods, saturated Cr etch depth/cycle of 1.1 and 1.5 ? /cycle were obtained for the chemical and physical anisotropic ALE, respectively, while maintaining near-infinite etch selectivities with various Si-based materials like silicon, silicon dioxide, and silicon nitride. The ALE technique can be used to precisely control the thickness of materials, including metals such as Cr, without any surface damage.
关键词： etch selectivity,adsorption,atomic layer etching,x-ray photoelectron spectroscopy,ion beam,chrome
更新于2025-09-04 15:30:14
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Effect of Deposition Method on Valence Band Offsets of SiO <sub/>2</sub> and Al <sub/>2</sub> O <sub/>3</sub> on (Al <sub/>0.14</sub> Ga <sub/>0.86</sub> ) <sub/>2</sub> O <sub/>3</sub>
摘要： There are often variations in reported valence band offsets for dielectrics on semiconductors and some of the reasons documented include metal or carbon contamination, interfacial disorder, variations in dielectric composition, thermal conditions, strain, and surface termination effects. In this paper we show that there are differences of up to 1 eV in band alignments for the common gate dielectrics SiO2 and Al2O3 on single crystal (Al0.14Ga0.86)2O3, depending on whether they are deposited by sputtering or Atomic Layer Deposition. In the case of Al2O3, this changed the band alignment from nested (type I) to staggered gap (type II). The valence band offset at each heterointerface was measured using X-Ray Photoelectron Spectroscopy and was determined to be ?0.85 ± 0.15 eV for sputtered Al2O3 and 0.23 ± 0.04 eV for ALD Al2O3 on β-(Al0.14Ga0.86)2O3, while for SiO2 it was 0.6 ± 0.10 eV for sputtered and 1.6 ± 0.25 eV for ALD. These results are consistent with recent results showing that the surface of Ga2O3 and related alloys are susceptible to severe changes during exposure to energetic ion environments.
关键词： Al2O3,(Al0.14Ga0.86)2O3,SiO2,valence band offsets,Atomic Layer Deposition,X-Ray Photoelectron Spectroscopy,sputtering
更新于2025-09-04 15:30:14