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Modification of TiO <sub/>2</sub> (1?1?0)/organic hole transport layer interface energy levels by a dipolar perylene derivative
摘要： Our photoemission study reveals that the work function of TiO2(1 1 0) decreases by up to 1.5 eV upon deposition of 9-(bis-(p-(tert-octyl)phenyl)amino)-perylene-3,4-dicarboxylic anhydride (BOPA-PDCA). This effect is attributed to a chemical reaction of TiO2(1 1 0) and the molecular anhydride group, as well as the molecular dipole. Analysis of the film thickness dependent photoemission and metastable atom electron spectroscopy data reveals that for low coverage the perylene backbone of BOPA-PDCA is almost parallel to the substrate surface and higher coverage leads to an orientational transition to essentially upright standing molecules. Comparing the energy-level alignment between TiO2(1 1 0) and the hole transport materials N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) without and with the BOPA-PDCA interlayer, we find that the perylene derivative has a positive impact on the level alignment for dye-sensitized solar cells with high open-circuit voltages.
关键词： solid state dye-sensitized solar cell,titanium dioxide,energy-level alignment,ultraviolet photoelectron spectroscopy,metastable atom electron spectroscopy,perylene
更新于2025-09-23 15:23:52
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The influence of nitrogen doping on the electronic structure of the valence and conduction band in TiO <sub/>2</sub>
摘要： X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS) provide a unique opportunity to probe both the highest occupied and the lowest unoccupied states in matter with bulk sensitivity. In this work, a combination of valence-to-core XES and pre-edge XAS techniques are used to determine changes induced in the electronic structure of titanium dioxide doped with nitrogen atoms. Based on the experimental data it is shown that N-doping leads to incorporation of the p-states on the occupied electronic site. For the conduction band, a decrease in population of the lowest unoccupied d-localized orbitals with respect to the d-delocalized orbitals is observed. As confirmed by theoretical calculations, the N p-states in TiO2 structure are characterized by higher binding energy than the O p-states which gives a smaller value of the band-gap energy for the doped material.
关键词： TiO2 doping,X-ray absorption spectroscopy,electronic structure analysis,X-ray emission spectroscopy
更新于2025-09-23 15:23:52
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Low-damage nitrogen incorporation in graphene films by nitrogen plasma treatment: Effect of airborne contaminants
摘要： Graphene films grown on copper by chemical vapor deposition were exposed to the late afterglow of a reduced-pressure N2 plasma sustained by microwave electromagnetic fields. X-ray photoelectron and Raman spectroscopies reveal extremely high incorporation of plasma-generated N atoms into the graphene film (N/C = 29%) while maintaining an unprecedentedly low-damage generation (D:G = 0.35-0.45) compared to the literature (0.5 to 2.5). The incorporation dynamics between graphene on copper and graphene on copper oxide are also compared and discussed. After transfer on SiO2/Si substrate, the N/C content decrease to only 6%. This reveals that a large part of the N atoms are weakly bonded to the graphene surface. Most of the nitrogen incorporation seems linked to the functionalization of weakly bonded hydrocarbons initially adsorbed from air exposure or carbon-nitrogen structures arising from plasma-surface interactions.
关键词： X-Ray photoelectron spectroscopy,Raman spectroscopy,graphene,downstream plasma treatment,N-incorporation
更新于2025-09-23 15:23:52
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Chemical Analysis of the Interface between Hybrid Organic-Inorganic Perovskite and Atomic Layer Deposited Al2O3
摘要： Ultrathin metal oxides prepared by atomic layer deposition (ALD) have gained utmost attention as moisture and thermal stress barrier layers in perovskite solar cells (PSCs). We have recently shown that 10 cycles of ALD Al2O3 deposited directly on top of the CH3NH3PbI3-xClx perovskite material, are effective in delivering a superior PSC performance with 18% efficiency (compared to 15% of the Al2O3-free cell) with a long-term humidity-stability of more than 60 days. Motivated by these results, the present contribution focuses on the chemical modification which the CH3NH3PbI3-xClx perovskite undergoes upon growth of ALD Al2O3. Specifically, we combine in situ Infrared (IR) spectroscopy studies during film growth, together with X-ray Photoelectron Spectroscopy (XPS) analysis of the ALD Al2O3/perovskite interface. The IR-active signature of the NH3+ stretching mode of the perovskite undergoes minimal changes upon exposure to ALD cycles, suggesting no diffusion of ALD precursor and co-reactant (Al(CH3)3 and H2O) into the bulk of the perovskite. However, by analyzing the difference between the IR spectra associated with the Al2O3 coated perovskite and the pristine perovskite, respectively, changes occurring at the surface of perovskite are monitored. The abstraction of either NH3 or CH3NH2 from the perovskite surface is observed as deduced by the development of negative N-H bands associated to its stretching and bending modes. The IR investigations are corroborated by XPS study, confirming the abstraction of CH3NH2 from the perovskite surface, whereas no oxidation of its inorganic framework is observed within the ALD window process investigated in this work. In parallel, the growth of ALD Al2O3 on perovskite is witnessed by the appearance of characteristic IR-active Al-O-Al phonon and (OH)-Al=O stretching modes. Based on the IR and XPS investigations, a plausible growth mechanism of ALD Al2O3 on top of perovskite is presented.
关键词： infrared spectroscopy,x-ray photoelectron spectroscopy,atomic layer deposition,Al2O3,perovskite
更新于2025-09-23 15:23:52
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Optical responses of BSA protein under re-entrant condensation in presence of trivalent ions
摘要： Fluorescence behavior of globular protein like BSA is studied under the re-entrant condensation in the presence of trivalent salts like YCl3 and LaCl3. BSA shows a re-entrant behaviour in solution where a specific turbid phase is formed between the two critical concentrations of the trivalent salts. Optical behaviours of proteins are explored by UV-Vis, photoluminescence and time resolved photoluminescence (TRPL) spectroscopy, whereas hydrodynamic size is obtained from the dynamic light scattering (DLS) technique. BSA shows maximum emission intensity at ≈ 338 nm for an excitation at 278 nm, however, the value of the peak intensity of emission gradually increases with the increase in salt concentration and becomes maximum at the turbid phase but for higher salt concentration as the re-dissolution takes place the emission intensity again decreases. TRPL study suggests that the decay time of BSA under re-entrant condensation is correlated with the salt concentration, whereas DLS study shows that the hydrodynamic size gradually increases up to a certain salt concentration where turbid phase is formed and then again decreases for higher salt concentrations. The variation of emission intensity of BSA nearly follows the modification of diffusion coefficient or hydrodynamic size and the phase transition behaviours.
关键词： UV-Vis spectroscopy,Bovine serum albumin,Tri-valent ions,Re-entrant condensation,Fluorescence spectroscopy
更新于2025-09-23 15:23:52
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Structural, morphological, composition and optical properties of undoped zinc oxide thin films prepared by spray pyrolysis method: effect of solution concentrations
摘要： The aim of this paper is the study of transparent undoped zinc oxide thin films obtained by spray pyrolysis technique on glass substrates heated at 350 °C from 0.1 to 0.4 mol solution concentrations using zinc acetate dehydrate as precursor. The X-ray diffraction patterns and Raman spectrometry with respect to Urbach energy and wurtzite structure, show that the maximum value of the high frequency intensity E2 and the optimal value of the optical gap are obtained at 0.2 mol concentration. Furthermore, an appropriate transparency is obtained and that makes these films suitable for photovoltaic windows layer cells.
关键词： X-ray diffraction,ultraviolet transmission spectroscopy,Raman spectroscopy,spray pyrolysis,undoped zinc oxide
更新于2025-09-23 15:23:52
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Incoherent Gain-Assisted Ring Enhanced Gas Absorption Spectroscopy
摘要： A novel incoherent gain-assisted ring enhanced spectroscopy technique is presented overcoming the need for precise optical alignment and high reflectivity dielectric mirrors. A gain medium pumped below the lasing threshold is used to improve the ring finesse and, thus, the interaction length. Two configurations are considered and compared. The first configuration is dual coupler ring with the source outside the ring and the gain medium inside the ring, while the second configuration is single coupler resonator with the gain medium acting as the source. The configurations are studied analytically and experimentally for different system parameters. The experimental results are obtained for a coupling ratio of 90/10. The broadband source is the amplified spontaneous emission of a semiconductor optical amplifier (SOA), while another SOA is used as the gain medium. Acetylene (C2H2) gas absorption is measured around 1540 nm wavelength. The output spectrum of the ring is measured using a 70 pm resolution. The interaction length is found to be enhanced by a factor of 9.35 and 44 in case of the dual coupler and single coupler resonator, respectively, compared to the direct absorption of the gas cell.
关键词： Gas spectroscopy,effective length enhancement,fiber sensors,finesse enhancement,incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS),active fiber cavities
更新于2025-09-23 15:23:52
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Evaluating the Surface Chemistry of Black Phosphorus during Ambient Degradation
摘要： Black Phosphorus (BP) is emerging as a promising candidate for electronic, optical and energy storage applications, however its poor ambient stability remains a critical challenge. Evaluation of few-layer liquid exfoliated BP during ambient exposure using x-ray photoelectron spectroscopy (XPS) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) allows its surface chemistry to be investigated. Oxidation of liquid exfoliated few-layer BP initially occurs through non-bridging oxide species, which convert to bridging oxide species after ambient exposure. We demonstrate the instability of these bridging oxide species, which undergo hydrolysis to form volatile phosphorus oxides and evaporate from the BP surface. FTIR spectroscopy, scanning transmission electron microscopy and atomic force microscopy were used to confirm the formation of liquid oxides through a continuous oxidation cycle that results in the decomposition of BP. Furthermore, we show that the instability of few-layer BP originates from the formation of bridging oxide species.
关键词： Fourier transform infrared spectroscopy,Black phosphorus,phosphorene,x-ray photoelectron spectroscopy,2D materials,degradation,ambient stability,oxidation
更新于2025-09-23 15:23:52
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X-ray photoelectron spectroscopy and Raman microscopy of a ferroan platinum crystal from the Kondyor Massif, Russian Far East
摘要： X-ray Photoelectron Spectroscopy was used to study a ferroan platinum crystal from the Kondyor Massif, Russian Far East. Prior to the X-ray Photoelectron Spectroscopic analyses, the nature of the crystal was confirmed by X-ray diffraction. The survey scan showed mainly the presence of Pt and Fe, with smaller amounts of O and Si. The high resolutions spectra of the Pt 4f and Fe 2p showed 18.3 atom% Fe in the crystal, which puts the composition on the lower boundary for ferroan platinum and confirms earlier analyses using other methods such as Scanning Electron Microscopy-Energy Dispersive X-ray analysis/microprobe. The binding energy of the Pt 4f5/2 was 74.0 eV and Pt 4f7/2 70.5 eV, while the Fe 2p3/2 for metallic Fe was observed at 707.2 eV. The Fe 2p3/2 for metallic Fe was significantly sharper than that of Fe 2p3/2 at 710.7 eV associated with surface material. The Raman spectrum was dominated by the Pt–Pt stretching mode at 253 cm?1. Changed orientation resulted in the observation of two bands at 127 and 139 cm?1, interpreted as being due to stretching modes of two Pt–Pt bonds with the third bond to Fe and Pt fixed. The presence of Ca-Fe-Al-Mg-Si-O on the surface was probably associated with the presence of a clinopyroxene. These minerals can be expected since the crystal came originally from a clinopyroxenite-dunite matrix. The spectra showed a variety of interferences, e.g. Al 2p with Pt 4f, Mg 2p with Fe 3p, and Ca 2p1/2 with Mg Auger, making exact determinations of the ratios of these elements difficult.
关键词： surface chemistry,platinum group minerals,X-ray photoelectron spectroscopy,Raman spectroscopy,Platinum
更新于2025-09-23 15:23:52
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Raman Spectroscopic and Microscopic Analysis for Monitoring Renal Osteodystrophy Signatures
摘要： Defining the pathogenesis of renal osteodystrophy (ROD) and its treatment efficacy are difficult, since many factors potentially affect bone quality. In this study, confocal Raman microscopy and parallel statistical analysis were used to identify differences in bone composition between healthy and ROD bone tissues through direct visualization of three main compositional parametric ratios, namely, calcium content, mineral-to-matrix, and carbonate-to-matrix. Besides the substantially lower values found in ROD specimens for these representative ratios, an obvious accumulation of phenylalanine is Raman spectroscopically observed for the first time in ROD samples and reported here. Thus, elevated phenylalanine could also be considered as an indicator of the disease. Since the image results are based on tens of thousands of spectra per sample, not only are the average ratios statistically significantly different for normal and ROD bone, but the method is clearly powerful in distinguishing between the two types of samples. Furthermore, the statistical outcomes demonstrate that only a relatively small number of spectra need to be recorded in order to classify the samples. This work thus opens the possibility of future development of in vivo Raman sensors for assessment of bone structure, remodeling, and mineralization, where different biomarkers are simultaneously detected with unprecedented accuracy.
关键词： Raman spectroscopy,bone composition,statistical analysis,renal osteodystrophy
更新于2025-09-23 15:23:52