Activation energy of water vapor and oxygen transmission through TiNxOy/PET gas barrier films

Titanium oxynitride (TiN_xO_y) films were deposited on polyethylene terephthalate (PET) substrates by means of a reactive radio frequency (RF) magnetron sputtering system in which the power density was the varied parameter. Experimental results show that the deposited TiN_xO_y films with a thickness of about 55 nm have similar contents of TiN, TiN_xO_y and TiO₂ bonds, although they are deposited at different power densities. The TiN_xO_y films deposited at a lower power density have fewer internal defects and grain boundaries and possess higher activation energy and a lower rate of water vapor and oxygen transmission through TiN_xO_y/PET films.     

Adsorption of glycine on a NiAl(1 1 0) alloy surface

The adsorption and desorption of glycine (NH₂CH₂COOH), vacuum deposited on a NiAl(1 1 0) surface, were investigated by means of Auger electron spectroscopy (AES), low energy electron diffraction (LEED), temperature-programmed desorption, work function (Δφ) measurements, and ultraviolet photoelectron spectroscopy (UPS). At 120 K, glycine adsorbs molecularly forming mono- and multilayers predominantly in the zwitterionic state, as evidenced by the UPS results. In contrast, the adsorption at room temperature (310 K) is mainly dissociative in the early stages of exposure, while molecular adsorption occurs only near saturation coverage. There is evidence that this molecularly adsorbed species is in the anionic form (NH₂CH₂COO⁻). Analysis of AES data reveals that upon adsorption glycine attacks the aluminium sites on the surface. On heating part of the monolayer adsorbed at 120 K is converted to the anionic form and at higher temperatures dissociates further before desorption. The temperature-induced dissociation of glycine (<400 K) leads to a series of similar reaction products irrespective of the initial adsorption step at 120 K or at 310 K, leaving finally oxygen, carbon and nitrogen at the surface. AES and LEED measurements indicate that oxygen interacts strongly with the Al component of the surface forming an “oxide”-like Al-O layer.     

c-Axis correlated extended defects and critical current in YBa2Cu3Ox films grown on Au and Ag-nano dot decorated substrates

We report measurements of critical current in YBa₂Cu₃O_x films deposited on SrTiO₃ substrates decorated with silver and gold nanodots. An increase in critical current in these films, in comparison with the films deposited on non-decorated substrates, has been achieved. We argue that this increase comes from the c-axis correlated extended defects formed in the films and originated from the nanodots. Additionally to creating extended defects, the nanodots pin them and prevent their exit from the sample during the film growth, thus keeping a high density of defects and providing a lower rate of decrease of the critical current with the thickness of the films. The best pinning is achieved in the samples with silver nanodots by optimising their deposition temperature. The nanodots grown at a temperature of a few hundred °C have a small diameter of a few nanometres and a high surface density of 10¹¹–10¹² particles/cm². We give evidence of c-axis correlated extended defects in YBa₂Cu₃O_x films by planar and cross-sectional atomic force microscopy, transmission electron microscopy and angle-dependent transport measurements of critical current.     

Characterization of ZnO thin films grown on various substrates by RF magnetron sputtering

In this study we investigated properties of ZnO thin films deposited on both oxygen-containing substrates and a substrate without oxygen content at various O₂/Ar reactant gas ratios. Deposition of ZnO on indium-tin oxide (ITO) resulted in the best crystallinity, whereas the least degree of crystallization was observed from ZnO deposited on glass. All the films were found to have compressive stress, which was relieved by annealing in O₂ environment. ZnO films deposited on glass revealed p-type conductivity when prepared at O₂/Ar ratio of 0.25 whereas those on SiN_x yielded p-type conductivity when prepared at O₂/Ar ratio of 4. In addition, shallower oxygen interstitial seemed to be found from films with better crystallinity. The largest shift in binding energy of Zn_2p3/2 was observed from ZnO prepared on glass at O₂/Ar ratio of 0.25, whereas that of O_1s was obtained from ZnO deposited on SiN_x at O₂/Ar ratio of 4. A model was proposed in terms of O₂ diffusion and hydrogen desorption in order to account for the observed property variations depending on substrates and O₂/Ar ratios.     

UPS and XPS studies of the chemisorption of O2, H2 AND H2O on reduced and stoichiometric SrTiO3(111) surfaces; The effects of illumination

About one monolayer of Ti³⁺ species is detectable at the surface of reduced SrTiO₃(111) single crystals by XPS and UPS. O₂, H₂ and H₂O have been adsorbed in the dark and the decrease on the concentration of the Ti³⁺ species has been monitored as a function of the gas exposures. Subsequent band gap illumination partially restores the Ti³⁺ initial concentration in the cases of O₂ and H₂ exposures but not in the case of H₂O. The Ti³⁺ photogeneration on the oxygen covered surface is associated with oxygen photodesorption as indicated by XPS and UPS. UPS measurements give evidence for surface hydroxylation resulting from water and hydrogen adsorption. The activity of the stoichiometric SrTiO₃(111) crystal face for O₂ and H₂ adsorption is very low when compared with the reduced SrTiO₃ samples.     

An investigation of the adsorption of oxygen and oxygen containing species on platinum by photoelectron spectroscopy

It is shown that XPS can detect 0.01 monolayers of adsorbed carbon or oxygen and can identify the chemical state of the adsorbed atom(s). Two states of adsorbed oxygen were resolved by thermal desorption spectroscopy and by XPS. The O 1s binding energies (^FE_B) were 530.2 and 533 eV below the platinum Fermi level for the strongly and weakly adsorbed states respectively. (^FE_B) did not vary with coverage. The resulting apparent variation of (^VE_B), the vacuum level referenced value, is discussed in terms of a simple model for the work function Φ which was measured in situ. UPS indicated that the weakly adsorbed state is probably molecular, with levels at 6.1, 9.3, 10.4 and l2.4 eV below the Fermi level. The main change in the UPS spectra produced by the strongly adsorbed state was a reduction of a peak close to the Fermi level.     

Gas barrier properties of titanium oxynitride films deposited on polyethylene terephthalate substrates by reactive magnetron sputtering

Titanium oxynitride (TiN_xO_y) films were deposited on polyethylene terephthalate (PET) substrates by means of a reactive radio frequency (RF) magnetron sputtering system in which the power density and substrate bias were the varied parameters. Experimental results show that the deposited TiN_xO_y films exhibited an amorphous or a columnar structure with fine crystalline dependent on power density. The deposition rate increases significantly in conjunction as the power density increases from 2 W/cm² to 7 W/cm². The maximum deposition rate occurs, as the substrate bias is −40 V at a certain power densities chosen in this study. The film's roughness slightly decreases with increasing substrate bias. The TiN_xO_y films deposited at power densities above 4 W/cm² show a steady Ti:N:O ratio of about 1:1:0.8. The water vapor and oxygen transmission rates of the TiN_xO_y films reach values as low as 0.98 g/m²-day-atm and 0.60 cm³/m²-day-atm which are about 6 and 47 times lower than those of the uncoated PET substrate, respectively. These transmission rates are comparable to those of DLC, carbon-based and Al₂O₃ barrier films. Therefore, TiN_xO_y films are potential candidates to be used as a gas permeation barrier for PET substrate.     

Studies of molecular oxygen adsorbed on Cu surfaces

Molecular oxygen adsorbed on (110) and polycrystalline Cu surfaces has been investigated by UPS, XPS, AES, HREELS and LEED. Molecularly adsorbed O₂ on the (110) surface shows the characteristic three-peak He II spectrum due to π_g, π_u and σ_g orbitals, accompanied by an O-O stretching frequency at 660 cm⁻¹. On the polycrystalline Cu surface, adsorbed O₂ shows the three peak He II spectra with a considerably smaller separation between the π_u and σ_g band and two O-O stretching bands at 610 and 880 cm⁻¹. O₂ adsorbed on the Cu(110) surface gives rise to a (1 × 1) LEED pattern and characteristic K π¹π¹ transition in the Auger spectrum.     

Electrical behaviour of SiOxNy thin films and correlation with structural defects

Silicon oxynitride thin films were deposited by reactive r.f. sputtering from a silicon target. Different Ar:O₂:N₂ gas atmospheres were used at fixed power density (3.18 W cm⁻²) and pressure (0.4 Pa) to obtain various film composition. Pt-SiO_xN_y-Pt sandwich type structure was realised for electrical property investigations. The C-V measurements showed the absence of a Schottky barrier and thus confirmed that Pt electrode provides an ohmic contact. The evolution of the current density showed a decrease of the film conductivity when the oxygen concentration in the films increases. The various layer composition leads to two different conduction mechanisms which were identified as space charge limited current (SCLC) and Poole-Frenkel effect. Finally, the structural defects of the films were studied by EPR analysis and the spin densities were correlated to both the composition and the electrical behaviour of the films.     

On the porosity of coldly condensed sers active Ag films: I. Characterization of the films by means of Xe adsorption

In this paper we report on the geometric structure of Ag films, deposited under UHV conditions and annealed at temperatures (T_an) ranging from 58 to 430 K, as deduced from UPS, AES, TDS and work function measurements of adsorbed xenon. The macroscopic work function of the bare films increases continuously from 4.25 eV (T_an = 60 K) to 4.72 eV (T_an = 330 K). Evidence is provided that coldly deposited Ag films are highly porous and that the pores persist up to T_an = 170 K, but are irreversibly healed between 170 and 250 K. The minimum thickness of the evaporated Ag films needed to develop these pores is found to be 50 Å. The width of the pores, which are most likely intercrystalline gaps, is estimated to be 5–15 Å. Besides the“macroscopic” pores the films contain atomic scale defects, which, in contrast to the pores, are healed continu- ously with increasing T_an. Films annealed at 330 K are composed of (111) grains with still a few percent of defect sites. The implications of these structural features on the adsorption properties of pyridine as well as on the interpretation of SERS results from such Ag films are dealt with in part II of this work.     

Thermal desorption study of Oxygen adsorption on Pt, Ag & Au films deposited on YSZ

The Thermal Desorption or Temperature Programmed Desorption (TPD) technique has been used for the study of oxygen adsorption on Pt, Ag and Au catalyst films deposited on YSZ. The catalyst film was deposited on the one side of the YSZ specimen while on the other side gold counter and reference electrodes were deposited, constructing a three-electrode electrochemical cell similar to those used in Electrochemical Promotion studies. Oxygen adsorption has been carried out either by exposing the samples to gaseous oxygen (gas phase adsorption) or by the application of a constant current between the catalyst/working electrode and the counter electrode (electrochemical adsorption) or by mixed gas phase and electrochemical adsorption. Oxygen adsorption was carried out at temperatures between 200 and 480 °C. After exposure to gaseous oxygen, normal adsorbed atomic oxygen species have been observed on Pt and Ag surfaces while there was no detectable amount of adsorbed oxygen on Au. Electrochemical O²⁻ pumping to Pt, Ag and Au catalyst films creates strongly bonded “backspillover” anionic oxygen, along with the more weakly bonded atomic oxygen. Electrochemical O²⁻ pumping to Pt, Ag and Au catalyst films in presence of preadsorbed oxygen creates strongly bonded “backspillover” anionic oxygen, with a concomitant pronounced lowering of the T_p of the more weakly bound preadsorbed atomic oxygen. The two oxygen species co-exist on the surface. The activation energy for oxygen desorption or, equivalently, the binding strength of adsorbed oxygen was found to decrease linearly with increasing catalyst potential, for all three metal electrodes. Paper presented at the 4th Euroconference on Solid State Ionics, Renvyle, Galway, Ireland Sept. 13–19, 1997     

Influence of oxygen on structural and optoelectronic properties of CdS thin film deposited by magnetron sputtering technique

In this study, CdS thin films with thicknesses of approximately 100 nm were deposited at a substrate temperature of 100 °C by a sputtering technique under two different ambient conditions—pure Ar ambient and Ar/O₂ (99:1) ambient—at deposition power densities of 1.0 and 2.0 W/cm², respectively The films were polycrystalline with a preferential orientation along the (002) crystal plane; however, the films deposited in the Ar/O₂ ambient exhibited reduced crystallinity. Furthermore, the crystallite sizes, micro-strains, and dislocation densities of the films were significantly affected by oxygen diffusion into the films’ crystal structures. The CdS films deposited in the Ar/O₂ ambient demonstrated higher optical transmittance and higher bandgaps. Morphologies observed from scanning electron microscopy images revealed that the grains of the films were also significantly affected by the oxygen present in the deposition ambient. Additionally, photoluminescence analysis revealed that the sulfur vacancies in the CdS films were partially filled by oxygen atoms, causing significant variations in the electrical properties of the films.     

氧分压对Mg掺杂ZnO薄膜结晶质量和光学特性的影响

利用脉冲激光沉积技术,通过改变沉积过程中的氧气压力,在蓝宝石(0001)基片上制备了一系列ZnMgO合金.通过X射线衍射、反射和透射光谱以及室温和变温荧光光谱,对薄膜的结构和光学性能进行了系统地表征,分析了工作气压对ZnMgO合金薄膜的结晶质量及光学特性的影响.研究结果表明:随着沉积环境中氧气压力的增大,ZnMgO薄膜的结晶质量下降,富氧环境下,与蓝宝石晶格平行的ZnO晶粒的出现是导致薄膜结晶质量下降的主要原因;相对于本征ZnO,不同氧气环境下沉积的ZnMgO薄膜的紫外荧光峰均出现了不同程度的蓝移.随着工 关键词： ZnO Mg掺杂 脉冲激光沉积 薄膜生长 光学特性     

Structural and luminescent characteristics of pulsed laser deposited Eu3+-doped Y2O3 thin films

Thin films of Eu-doped Y₂O₃ were deposited using the pulsed laser ablation technique on amorphous fused silica substrates. The effect of oxygen partial pressure (pO₂) and substrate temperature on the structural and optical characteristics of the deposited films were investigated. All the deposited films were crystalline, showing preferred orientation along the (111) plane, irrespective of oxygen partial pressure and substrate temperature. The film deposited at 0.005?mbar pO₂ exhibited better crystallinity with minimum FWHM at a substrate temperature of 600°C. All the films deposited at various substrate temperatures and different partial pressure (at 600°C) exhibited a red luminescence peak at 615?nm corresponding to the ⁵D₀–⁷F₁ transition in Eu³⁺. Photoluminescence excitation spectra exhibited two bands, one corresponding to band to band excitation (212?nm) of the host and the other to charge transfer band excitation (245?nm). A microstructure analysis revealed that surface roughness of the as-deposited films increases with increase in oxygen partial pressure.     

The effect of oxygen pressure on the structure, morphology and photoluminescence intensity of pulsed laser deposited Gd2O2S:Tb3+ thin film phosphor

Luminescent Gd₂O₂S:Tb³⁺ phosphor thin films were grown on Si (100) substrates, using the pulsed laser deposition technique. The films were grown in 100 to 300 mTorr oxygen gas (O₂) atmospheres when the substrate temperature was kept constant at 400 or 600°C. The effect of the O₂ ambient on the structure and morphological properties of the films were analyzed using x-ray diffraction (XRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM), respectively. Spherical nanoparticles deposited on the Si (100) substrates were shown to crystallize in the hexagonal structure of Gd₂O₂S. The photoluminescence (PL) spectra of all the films were characterized by a stable green emission peak with a maximum at 545 nm. Improved PL intensity was observed from the films deposited at higher oxygen pressures and higher substrate temperatures. Particles sizes of the nanoparticles deposited under the different conditions varied between 19 and 36 nm for the different samples. Smaller and more densely packet particles were produces at the higher O₂ pressures and the higher temperature.     

H2O interaction with clean and oxygen precovered Ni(110)

The interaction of water vapour with clean as well as with oxygen precovered Ni(110) surfaces was studied at 150 and 273 K, using UPS, ΔΦ, TDS, and ELS. The He(I) (He(II)) excited UPS indicate a molecular adsorption of H₂O on Ni(110) at 150 K, showing three water-induced peaks at 6.5, 9.5 and 12.2 eV below E_F (6.8, 9.4 and 12.7 eV below E_F). The dramatic decrease of the Ni d-band intensity at higher exposures, as well as the course of the work function change, demonstrates the formation of H₂O multilayers (ice). The observed energy shift of all water-induced UPS peaks relative to the Fermi level (ΔE_max = 1.5 eVat 200 L) with increasing coverage is related to extra-atomic relaxation effects. The activation energies of desorption were estimated as 14.9 and 17.3 kcal/mole. From the ELS measurements we conclude a great sensitivity of H₂O for electron beam induced dissociation. At 273 K water adsorbs on Ni(110) only in the presence of oxygen, with two peaks at 5.7 and 9.3 eV below E_F (He(II)), being interpreted as due to hydroxyl species (OH)^δ? on the surface. A kinetic model for the H₂O adsorption on oxygen precovered Ni(110) surfaces is proposed, and verified by a simple Monte Carlo calculation leading to the same dependence of the maximum amount of adsorbed H₂O on the oxygen precoverage as revealed by work function measurements. On heating, some of the (OH)^δ? recombines and desorbs as H₂O at ? 320 K, leaving behind an oxygen covered Ni surface.     

Effect of process parameters on surface morphology and characterization of PE-ALD SnO2 thin films for gas sensing

Tin dioxide (SnO₂) thin films were deposited by plasma enhanced-atomic layer deposition (PE-ALD) on Si(1 0 0) substrate using dibutyl tin diacetate (DBTA) ((CH₃CO₂)₂Sn[(CH₂)₃-CH₃]₂) as precursor. The process parameters were optimized as a function of substrate temperature, source temperature and purging time. It is observed that the surface phenomenon of the thin films was changed with film thickness. Atomic force microscopy (AFM) images and X-ray diffraction (XRD) pattern were used to observe the texture and crystallanity of the films. The films deposited for 100, 200 and 400 cycles were characterized by XPS to determine the chemical bonding properties. XPS results reveal that the surface dominant oxygen species for 100, 200 and 400 cycles deposited films are O₂⁻, O⁻ and O²⁻, respectively. The 200 cycles film has exhibited highest concentration of oxygen (O⁻) species before and after annealing. Conductivity studies revel that this film has best adsorption strength to the oxygen ions forming on the surface. The sensor with 200 cycles SnO₂ thin film has shown highest sensitivity to CO gas than other films. A correlation between the characteristics of Sn3d_5/2 and O1s XPS spectra before and after annealing and the electrical behavior of the SnO₂ thin films is established.     

Investigation of electrical and optical properties of ZnO thin films grown with O<Subscript>2</Subscript>/O<Subscript>3</Subscript> gas mixture

The electrical and optical properties of ZnO thin films grown with an O₂/O₃ gas mixture are compared with samples grown with pure oxygen gas. The ZnO films were grown on sapphire(0001) by pulsed laser deposition. The residual background carrier concentration is reduced by using an O₂/O₃ gas mixture as compared to pure molecular oxygen. In particular, a one order of magnitude reduction in residual background carrier density (6.15×10¹⁶ cm^-3) is achieved by using an O₂/O₃ gas mixture. The lower donor defect density is attributed to the generation of acceptor defects compensating for the residual donor defects. Photoluminescence results show that the deep level emission increased and the band edge emission decreased for the ZnO films grown with ozone, as compared to the samples grown with pure oxygen gas. PACS 73.61.Ga; 78.55Et; 81.05 Dz; 81.15.Fg     

Correlation of plume dynamics and oxygen pressure with VO2 stoichiometry during pulsed laser deposition

Vanadium dioxide thin films have been deposited on Corning glass substrates by a KrF laser ablation of V₂O₅ target at the laser fluence of 2 J?cm^?2. The substrate temperature and the target-substrate distance were set to 500 ^°C and 4 cm, respectively. X-ray diffraction analysis showed that pure VO₂ is only obtained at an oxygen pressure range of 4×10^?3–2×10^?2 mbar. A higher optical switching contrast was obtained for the VO₂ films deposited at 4×10^?3–10^?2 mbar. The films properties were correlated to the plume-oxygen gas interaction monitored by fast imaging of the plume.     

Defect sites in thin films of germanium dioxide irradiated with silicon ions

Optical transmission spectra of GeO₂ films irradiated with silicon ions and subjected to postimplantation annealing in the regime of silicon nanocrystal formation are analyzed. It is shown that point defects form in the films after irradiation with doses D ～ 10²⁰ m^?2: germanium electron centers, neutral oxygen vacancies, and Ge²⁺ centers, which have been annealed at a temperature of 1000°C for an hour. At D ≥ 1 × 10²¹ m^?2, more complex defects arise in the films, which are only partially annealed under the same conditions.