Preparation of visible-light responsive PF-codoped TiO2 nanotubes

Fabrication of PF-codoped TiO₂ nanotubes was carried out using a one-step electrochemical anodization process by tailoring the composition of the electrolyte with the aim of PF-codoping to extend the optical absorption of TiO₂ to the visible-light region. The as-prepared PF-codoped TiO₂ nanotubes were characterized by SEM, XPS, and UV-vis diffuse reflectance absorption spectra (DRS). The results showed that the tube diameter of the nanotubes was approximately 100 nm and the tube length was approximately 510 nm. The phosphorus and fluorine were successfully doped into TiO₂ nanotubes, as evidenced by XPS. Moreover, the PF-codoped samples displayed remarkably strong visible-light response.     

Influence of thermal treatment of low dielectric constant SiOC(H) films using MTES/O2 deposited by PECVD

Low dielectric constant SiOC(H) films are deposited on p-type Si(100) substrates by plasma enhanced chemical vapor deposition (PECVD) using methyltriethoxysilane (MTES, C₇H₁₈O₃Si) and oxygen gas as precursors. The SiOC(H) films are deposited at room temperature, 100, 200, 300 and 400 °C and then annealed at 100, 200, 300 and 400 °C temperatures for 30 min in vacuum. The influence of deposition temperature and annealing on SiOC(H) films are investigated. Film thickness and refractive index are measured by field emission scanning electron microscopy and ellipsometry, respectively. Chemical bonding characteristics of as-deposited and annealed films are investigated by Fourier transform infrared (FTIR) spectroscopy in the absorbance mode. As more carbon atoms are incorporated into the SiOC(H) films, both film density and refractive index are decreased due to nano pore structure of the film. In the SiOC(H) film, CH₃ group as an end group is introduced into OSiO network, thereby reducing the density to decrease the dielectric constant thereof. The dielectric constant of SiOC(H) film is evaluated by C-V measurements using metal-insulator-semiconductor (MIS), Al/SiOC(H)/p-Si structure and it is found to be as low as 2.2 for annealed samples deposited at 400 °C.     

Effect of phase structures on the formation rate of hydroxyl radicals on the surface of TiO2

To study the relationship between the phase structures of TiO₂ and the photoinduced hydroxyl radicals (OH), TiO₂ nanocrystallines were synthesized by a hydrolysis-precipitate method using tetrabutylorthotitanate (TBOT) as precursor, and then calcined at 450, 600, 700, 800 and 900 °C for 2 h, respectively. The calcined samples were characterized by X-ray diffraction and N₂ sorption. The formation rate of OH on the surface of UV-illuminated TiO₂ was detected by the photoluminescence (PL) technique using terephthalic acid as a probe molecule. The results show that with increasing calcined temperatures, the amorphous (Am) TiO₂ precursor begins to turn into anatase (A) at 450 °C and rutile (R) phase appears at 600 °C, which is completely turned into the rutile phase at 900 °C. The BET specific surface areas of the catalyst decrease as the calcined temperatures increase. TiO₂ sample calcined at 600 °C, with a mixed phase of anatase and rutile, shows the highestOH formation rate, and the order of the OH formation rate is as follows: A+R>A>R>Am. Phase structures of TiO₂ play a more important role than specific surface areas in the OH formation rate. Two phase structure of anatase and rutile with a proper ratio is beneficial to the OH formation due to decrease of the combination rate of photo-generated electrons and holes. Our experimental result implies that the mixed phase of anatase and rutile can markedly enhance the photocatalytic activity of TiO₂.     

Low temperature catalytic performance of nanosized TiNiO for oxidative dehydrogenation of propane to propene

Nanosized TiNiO catalysts prepared by a modified sol-gel method have been investigated in the oxidative dehydrogenation of propane (ODP) to propene. At 300 °C the yield to propene of 12.1% was obtained on 9.1 wt.% TiNiO catalyst with the selectivity of 43%. The continued variety of lattice parameter and variation of chemical value of nickel and titanium ion on the surface indicates that there are strong interactions of TiO₂ and NiO. The decreased low temperature oxygen desorption and the weaker reducibility seems to be responsible for the decreased activity and enhanced selectivity of propane oxidative dehydrogenation over TiNiO catalysts.     

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO₃BaF₂WO₃ and the binary system NaPO₃WO₃ with high concentrations of WO₃ (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L_I and L_III absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO₆) and that these films are free of tungstate tetrahedral units (WO₄). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO₃ increases and the formation of POW bonds in the films network indicating the intermediary behavior of WO₆ octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of WO⁻ and WO terminal bonds and a progressive apparition of WOW bridging bonds for the most WO₃ concentrated samples (above 40% molar) attributed to the formation of WO₆ clusters.     

Pulsed laser ablation of borax target in vacuum and hydrogen DC glow discharges

The aim of our experiment was to produce a material with BH bonds for applications in hydrogen storage and generation. By using KrF excimer laser (λ = 248 nm) ablation of borax (Na₂B₄O₇) target, thin films were deposited on KBr and silicon substrates. Ablation was performed both in vacuum and in hydrogen atmosphere. DC glow discharge technique was utilized to enhance hydrogen gas ionization. Experiments were performed using laser fluence from 5 to 20 J/cm². Films were deposited under gas pressure of 1 × 10⁻⁵ to 5 × 10⁻² mbar and substrate temperatures of 130-450 °C. Scanning electron microscopy analysis of films showed presence of circular particulates. Film thickness, roughness and particulates number increased with increase in laser fluence. Energy dispersive X-ray spectroscopy analysis shows that sodium content in the particulates is higher than in the target. This effect is discussed in terms of atomic arrangements (both at surface and bulk) in systems where ionic and covalent bonds are present and by looking at the increased surface/bulk ratio of the particulates with respect to the deposited films. The Fourier transform infrared spectroscopy measurements showed presence of BO stretching and BOB bending bonds. Possible reasons for absence of BH bonds are attributed to binding enthalpy of the competing molecules.     

Ab initio studies of electronic spectra of the linear aluminum-bearing carbon chains AlC2nH (n = 1-5)

Geometries and stabilities of the linear aluminum-bearing carbon chains AlC_2nH (n = 1-5) in their ground states have been explored by the DFT-B3LYP and RCCSD(T) methods. Structures of the X¹Σ⁺ and 1¹Π electronic states have also been optimized by the CASSCF approach. The studies indicate that these species have single-triple bond alternate pattern, AlCCCC?CCH, and the electronic excitation from X¹Σ⁺ to 1¹Π leads to the shortening of the AlC bonds. The vertical excitation energies of the 1¹Π ← X¹Σ⁺ and 2¹Π ← X¹Σ⁺ transitions for AlC_2nH (n = 1-5) have been investigated by the CASPT2, EOM-CCSD, and TD-B3LYP levels of theory with the cc-pVTZ basis set, respectively. CASPT2-predicted 1¹Π ← X¹Σ⁺ transition energies are 3.57, 3.44, 3.33, 3.26, and 3.21 eV, respectively. For AlC₂H, our estimate agrees very well with the experimental value of 3.57 eV. In addition, the AlC bond dissociation energies and the exponential-decay curves for these vertical excitation energies are also discussed.     

UV assisted oxidation and nitridation of hafnia based thin films for alternate gate dielectric applications

The synergistic effects of NH₃ ambient and ultraviolet illumination on the dielectric properties of hafnia based gate dielectrics are reported in this paper. The films were processed at relatively low temperatures (∼400 °C) by pulsed laser ablation and UV oxidation technique. UV illumination and the NH₃ ambient created a thin and a denser interfacial layer (at the film-Si interface) comprised of HfSiON bonding. As a result of the interfacial layer modification, a leakage current density lower than 10⁻⁴ A/cm² and a dielectric constant of ∼21.7 were extracted from the best samples processed in NH₃ and under UV illumination. The nitrogen doped HfO₂ also exhibited a thinner interfacial layer (∼12 Å) in comparison to the films processed without NH₃ ambient.     

Near infrared spectroscopy of organic acids: comparing OH and CH oscillator frequencies and intensities

This work investigates the vibrational spectroscopy of a series of organic acids, CH₃(CH₂)_nCOOH (n = 1-5), previously unobserved in the IR and near-IR (2000-15 000 cm⁻¹). The work obtains frequencies and relative intensities for all OH and CH stretching transitions. Comparison of the frequencies and intensities of CH and OH stretching transitions reveal interesting trends in acid chain length that are discussed. Literature values for acetic acid (CH₃COOH) and formic acid (HCOOH) are used to gain a broader understanding for the spectroscopy of the organic acids CH₃(CH₂)_nCOOH. The observation of several combination bands involving the CH and OH stretching vibrations and possible rotational isomer and hot band transitions are reported.     

S180 cell growth on low ion energy plasma treated TiO2 thin films

X-ray photoelectron spectroscopy (XPS) was used to characterise the effects of low energy (<2 eV) argon ion plasma surface modification of TiO₂ thin films deposited by radio frequency (RF) magnetron sputter system. The low energy argon ion plasma surface modification of TiO₂ in a two-stage hybrid system had increased the proportion of surface states of TiO₂ as Ti³⁺. The proportion of carbon atoms as alcohol/ether (COX) was decreased with increase the RF power and carbon atoms as carbonyl (CO) functionality had increased for low RF power treatment. The proportion of C(O)OX functionality at the surface was decreased at low power and further increase in power has showed an increase in its relive proportion at the surface. The growth of S180 cells was observed and it seems that cells are uniformly spreads on tissue culture polystyrene surface and untreated TiO₂ surfaces whereas small-localised cell free area can be seen on plasma treated TiO₂ surfaces which may be due to decrease in C(O)OX, increase in CO and active sites at the surface. A relatively large variation in the surface functionalities with no change in the surface roughness was achieved by different RF plasma treatments of TiO₂ surface whereas no significant change in S180 cell growth with different plasma treatments. This may be because cell growth on TiO₂ was mainly influenced by nano-surface characteristics of oxide films rather than surface chemistry.     

The surface modification of nanoporous SiOx thin films with a monofunctional organosilane

The surfaces of nanostructured, porous SiO_x/Si (air-oxidized Si) and SiO_x thin films, deposited by excimer laser ablation in He and He + O₂ gas ambients, respectively, have been modified by the deposition of a monofunctional organosilane. They were characterized using photoacoustic Fourier-transform infrared (FTIR) X-ray photoelectron (XPS) spectroscopies, and field-emission scanning electron microscopy (FESEM). Photoacoustic FTIR analysis indicates that the organosilane has hydrolyzed to form a silanol, which has chemically reacted with SiO_x through its surface silanol (SiOH) group, to form siloxane (SiOSi) structures. An enhanced IR spectral signal is found, due to the expansion and contraction of both the pores of the solid and the gas within them.     

Pre-treatments applied to oxidized aluminum surfaces to modify the interfacial bonding with bis-1,2-(triethoxysilyl)ethane (BTSE): Part I. High-purity Al with native oxide

A remote microwave-generated H₂ plasma and heating to 250 °C were separately used to modify high-purity oxidized aluminum surfaces and to assess whether these treatments can help enhance adhesion with bis-1,2-(triethoxysilyl)ethane (BTSE) coatings. Different initial oxide surfaces were considered, corresponding to the native oxide and to surfaces formed by the Forest Products Laboratory (FPL) treatment applied for either 15 or 60 min. BTSE is applied from solution at pH 4, and competing processes of etching, protonation (to form OH groups) and coupling (to form AlOSi interfacial bonds) occur at the solid-liquid interface. Scanning electron microscopy (SEM) was used to determine how the topographies of the modified Al surfaces changed with the different pre-treatments and with exposure to a buffer solution of pH 4. Secondary-ion mass spectrometry (SIMS) was used to determine the direct amount of AlOSi interfacial bonds by measuring the ratio of peak intensities 71-70 amu, while X-ray photoelectron spectroscopy (XPS) was used to determine the overall strength of the silane coating adhesion by measuring the Si 2p signals before and after application of an ultrasonic rinse to the coated sample. Measured Al 2p and O 1s spectra helped assess how the different pre-treatments modified the various Al oxidized surfaces prior to BTSE coating. Pre-treated samples that showed increased AlOSi bonding after BTSE coating corresponded to surfaces, which did not show evidence of significant etching after exposure to a pH 4 environment. This suggests that such surfaces are more receptive to the coupling reaction during exposure to the BTSE coating solution. These surfaces include all H₂ plasma-treated samples, the heated native oxide and the sample that only received the 15 min FPL treatment. In contrast, other surfaces that show evidence of etching in pH 4 environments are samples that received lower amounts of AlOSi interfacial bonding. Overall, heating improved the BTSE adhesive bonding for the native Al oxide, while H₂ plasma treatment improved the BTSE bonding for surfaces that had initially been FPL-treated for 15 and 60 min.     

Asymmetric surface modification of poly(ethylene terephthalate) film by CF4 plasma immersion

Poly(ethylene terephthalate) (PET) films were treated with CF₄ plasma immersion. The samples were processed at different RF powers and treatment time. The surface modification of PET films was evaluated by water contact angle (CA), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). Decrease in contact angle of both sides of PET films was observed under mild treatment conditions. However, as raising treatment power and/or time, the change in contact angle between the two sides of PET films was different. The relatively hydrophobic and hydrophilic surfaces were being in situ formed on the two sides of PET films, respectively. And the extreme values of water contact angle reached 108.63 and 7.56°, respectively. XPS analyses revealed that there was a substantial incorporation of fluorine and/or oxygen atoms in both side surfaces. The relative chemical composition of the C (ls) spectra's showed the incorporation of non-polar fluorine-based functionalities (i.e. CFCF_n, CF₂ or CF₃ groups) and polar oxygen-based functionalities (i.e. COOH or OH groups) in the surfaces. Correlation between the plasma parameters and the surface modification of PET films is also discussed.     

Chemical reaction of sputtered Cu film with PI modified by low energy reactive atomic beam

Polyimide (PMDA-ODA) surface was irradiated by low energy reactive atomic beam with energy 160-180 eV to enhance the adhesion with metal Cu film. O₂⁺ and N₂⁺ ions were irradiated at the fluence from 5 × 10¹⁵ to 1 × 10¹⁸ cm⁻². Wetting angle 78° of distilled deionized (DI) water for bare PI was greatly reduced down to 2-4° after critical ion flounce, and the surface energy was increased from 37 to 81.2 erg/cm. From the analysis of O 1s core-level XPS spectra, such improvement seemed to result from the increment of hydrophilic carbonyl oxygen content on modified PI surface. To see more carefully correlation of the peel strength with interfacial reaction between Cu and PI, flexible copper clad laminate with Cu (9 μm)/Cu (200 nm) on modified PI substrate (25 μm) was fabricated by successive sputtering and electroplating. Firstly, peel strength was measured by using t-test and it was largely increased from 0.2 to 0.5 kgf/cm for Ar⁺ only irradiated PI to 0.72-0.8 kgf/cm for O₂⁺ or N₂O⁺ irradiated PI. Chemical reaction at the interface was reasoned by analyzing C 1s, O 1s, N 1s, and Cu 2p core-level X-ray photoelectron spectroscopy over the as-cleaved Cu-side and PI side surface through depth profiling. From the C 1s spectra of cleaved Cu-side, by the electron transfer from Cu to carbonyl oxygen, carbonyl carbon atom became less positive and as a result shifted to lower binding energy not reaching the binding energy of C₂ and C₃. The binding energy shift of the peak C₄ as small as 1.7 eV indicates that carbonyl oxygen atoms were not completely broken. From the analysis of the O 1s spectra, it was found that new peak at 530.5 eV (O₃) was occurred and the increased area of the peak O₃ was almost the same with reduced area of the peak carbonyl oxygen peak O₁. Since there was no change in the relative intensity of ether oxygen (O₂) to carbonyl oxygen (O₁), and thus O₃ was believed to result from Cu oxide formation via a local bonding of Cu with carbonyl oxygen atoms. Moreover, from X-ray induced Auger emission spectra Cu LMM which was very sensitive to chemical bonding, Cu oxide or CuOC complex formation instead of CuNO complex was clearly identified by the observation of the peak at 570 eV at higher 2 eV than that of metal Cu. In conclusion, when Cu atoms were sputtered on modified PI by low energy ion beam irradiation, it can be suggested that two Cu atoms locally reacted with carbonyl oxygen in PMDA units and formed Cu⁺O⁻C complex linkage without being broken from carbon atoms and thus the chemically bound Cu was in the form of Cu₂O.     

An XPS study of pulsed plasma polymerised allyl alcohol film growth on polyurethane

The growth of highly functionalised poly allyl alcohol films by pulsed plasma polymerisation of CH₂CHCH₂OH on biomedical grade polyurethane has been followed by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Film thickness is observed to increase approximately linearly with plasma modification time, suggesting a layer-by-layer growth mode of poly allyl alcohol. Water contact angle measurements reveal the change in the surface free energy of wetting decreases linearly with plasma modification up to the monolayer point after which a constant limiting value of −24 mJ m⁻² was attained. Films prepared at 20 W plasma power with a duty cycle of 10 μs:500 μs exhibit a high degree of hydroxyl (OH) retention with minimal fragmentation of the monomer observed. Increasing the plasma power up to 125 W is found to improve OH retention at the expense of ether formation generating films close to the monomer stoichiometry. Duty cycle plays an important role in controlling both film composition and thickness, with longer off times increasing OH retention, while longer on times enhance allyl alcohol film growth.     

Enhancement of Ti-containing hydrogenated carbon (TiC:H) films by high-power plasma-sputtering

Ti-containing amorphous hydrogenated carbon (TiC:H) thin films were deposited on stainless steel SS304 substrates by high-power pulsed magnetron sputtering (HPPMS) in an atmosphere of mixed Ar and C₂H₂ gases using titanium metal as the cathodic material. The multilayer structure of the deposited film had a TiTiCDLC gradient to improve adhesion and reduce residual stress. This study investigates the effects of substrate bias and target-to-substrate distance on the mechanical properties of TiC:H films. Film properties, including composition, morphology, microstructure, mechanical, and tribology, were examined by glow discharge spectroscopy (GDS), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, and a nanoindenter and a pin-on-disk tribometer. Experiments revealed impressive results.     

Surface modification of poly(propylene carbonate) by oxygen ion implantation

Poly(propylene carbonate) (PPC) was implanted by oxygen ion with energy of 40 keV. The influence of experimental parameters was investigated by varying ion fluence from 1 × 10¹² to 1 × 10¹⁵ ions/cm². XPS, SEM, surface roughness, wettability, hardness, and modulus were employed to investigate structure and properties of the as-implanted PPC samples. Eight chemical groups, i.e., carbon, CH, COC, CO, OCO, CO, , and groups were observed on surfaces of the as-implanted samples. The species and relative intensities of the chemical groups changed with increasing ion fluence. SEM images displayed that irradiation damage was related strongly with ion fluence. Both surface-recovering and shrunken behavior were observed on surface of the PPC sample implanted with fluence of 1 × 10¹⁵ ions/cm². As increasing ion fluence, the surface roughness of the as-implanted PPC samples increased firstly, reached the maximum value of 159 nm, and finally decreased down the minimum value. The water droplet contact angle of the as-implanted PPC samples changed gradually with fluence, and reached the minimum value of 70° with fluence of 1 × 10¹⁵ ions/cm². The hardness and modulus of the as-implanted PPC samples increased with increasing ion fluence, and reached their corresponding maximum values with fluence of 1 × 10¹⁵ ions/cm². The experimental results revealed that oxygen ion fluence closely affected surface chemical group, morphology, surface roughness, wettability, and mechanical properties of the as-implanted PPC samples.     

Effect of oxidation on the optical and surface properties of AlGaN

The chemical properties of Al_xGa_1−xN surfaces exposed to air for different time periods are investigated by atomic force microscopy (AFM), photoluminescence (PL) measurement and X-ray photoelectron spectroscopy (XPS). PL and AFM results show that Al_xGa_1−xN samples exhibit different surface characteristics for different air-exposure times and Al contents. The XPS spectra of the Al 2p and Ga 2p core levels indicate that the peaks shifted slightly, from an AlN to an AlO bond and from a GaN to a GaO bond. All of these results show that the epilayer surface contains a large amount of Ga and Al oxides.     

Improvement of photoluminescence properties of porous silicon by silica passivation

Porous silicon (PS) was passivated by silica film using a sol-gel method; the photoluminescence (PL) properties were significantly improved; namely, PL intensity and stability increased and PL peak shifted to shorter wavelength. Scanning electron microscope (SEM) and Fourier transformed infrared spectroscope (FTIR) results indicated that silica passivation produced a compact film on the PS surface and modified the surface state of PS. The number of stable surface bonds (HSiO₃, HSiSiO₂ and H₂SiO₂) increased due to the oxidation of SiH back-bonds during the gelation process, and thus the PL intensity and stability were improved. Moreover, the blue-shift of PL peak was determined due to the increase in the ratio of SiO/SiH.