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.     

Effects of O2 and H2O plasma immersion ion implantation on surface chemical composition and surface energy of poly vinyl chloride

Oxygen and water plasma immersion ion implantation (PIII) was used to modify poly vinyl chloride (PVC) to enhance oxygen-containing surface functional groups for more effective grafting. The modified surfaces were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and contact angle measurements. Our experimental results show that both oxygen and water PIII can greatly improve the O to C ratios on the surface. The optimal plasma processing conditions differ for the two treatments. The hydrophilicity and surface energy of the plasma-implanted PVC are also improved significantly. Our results indicate that O₂ and H₂O PIII increase both the polar and dispersion interactions and consequently the surface energy. It can be explained by the large amount of oxygen introduced to the surface and that many CC bonds are transformed into more polar oxygen containing functional groups.     

Shuttle-like ZnO nano/microrods: Facile synthesis, optical characterization and high formaldehyde sensing properties

Shuttle-like ZnO nano/microrods were successfully synthesized via a low temperature (80 °C), “green” (without any organic solvent or surfactant) and simple hydrothermal process in the solution of zinc chloride and ammonia water. X-ray diffraction and Raman spectroscopy indicated that the ZnO nano/microrods are a well-crystallized hexagonal wurtzite structure. Yet photoluminescence analysis showed that abundant intrinsic defects (52.97% electron donor defects and 45.49% electron acceptor defects) exist on the surface of ZnO crystals. Gas sensors based on the shuttle-like ZnO nano/microrods exhibited high sensitivity, rapid response-recovery and good selectivity to formaldehyde in the range of 10-1000 ppm at an optimum operating temperature of 400 °C. Through applying linear fitting to the plot of sensitivity versus formaldehyde concentration in logarithmic forms, the chemisorbed oxygen species on the ZnO surface were found to be O²⁻ (highly active among O₂, O₂⁻ and O⁻ species). Notably, formaldehyde can be easily distinguished from acetaldehyde with a selectivity of about 3. The high formaldehyde sensitivity is mainly attributed to the synergistic effect of abundant electron donor defects (52.97%) and highly active oxidants (surface adsorbed O²⁻ species) co-existed on the surfaces of ZnO.     

Low-Temperature Oxidation of Polycrystalline Silver in Water Vapor

X-ray photoelectron spectroscopy and electron Auger spectroscopy are used to study the surface layers of polycrystalline silver after exposure to water vapor. It is shown that molecular oxygen, atomic oxygen in the composition of AgO and Ag₂O, and silver in the zero-valence state are present in the surface region, and also the presence of associated oxygen forms in Ag⁰–O _x -peroxide, superoxide, and ozonide structures is possible.     

Infrared spectroscopic study of alkyl aldehydes adsorbed on cations supported by layer silicate

The self-supported film specimen of Wyoming montmorillonite as a layer silicate exchanged by cations, Li⁺, Na⁺, K⁺, Ca²⁺, Ni²⁺, and Al³⁺ were allowed to contact acetaldehyde, acrolein and crotonaldehyde within the heatable gas cell. Adsorption mechanism of alkyl aldehydes on cations supported by layer silicate was studied by means of infrared spectroscopy and X-ray. The infrared spectra between 4000 and 1200 cm⁻¹ at different pressures of adsorbates indicated bond formation through carbonyl oxygen. The intensity of the stretching OH was analyzed and resonance form of cationic hydroxyl was proposed as an adsorption site. The carbonyl stretching band, which shifted about 130 cm⁻¹ to lower frequencies was observed only for Ni²⁺, Ca²⁺, and Al³⁺ supported by layer silicate and was attributed to >CO···Mⁿ⁺ complex formation. A sharp band, which appeared as a shoulder at 1722 for acetaldehyde and 1690 for acrolein and crotonaldehyde, was responsible for the interaction of carbonyl with surface hydroxyl. The second broad band, which appeared at about 1710-1660, was responsible for hydrogen bonding between carbonyl oxygen and cationic hydroxyl group.     

Protein imprinting and recognition via forming nanofilms on microbeads surfaces in aqueous media

In this paler, we present a technique of forming nanofilms of poly-3-aminophenylboronic acid (pAPBA) on the surfaces of polystyrene (PS) microbeads for proteins (papain and trypsin) in aqueous. Papain was chosen as a model to study the feasibility of the technique and trypsin as an extension. Obtained core-shell microbeads were characterized using scanning electron microscopy (SEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and BET methods. The results show that pAPBA formed nanofilms (60-100 nm in thickness) on the surfaces of PS microbeads. The specific surface area of the papain-imprinted beads was about 180 m² g⁻¹ and its pore size was 31 nm. These imprinted microbeads exhibit high recognition specificity and fast mass transfer kinetics. The specificity of these imprinted beads mainly originates from the spatial effect of imprinted sites. Because the protein-imprinted sites were located at, or close to, the surface, the imprinted beads have good site accessibility toward the template molecules. The facility of the imprinting protocol and the high recognition properties of imprinted microbeads make the approach an attractive solution to problems in the field of biotechnology.     

Oxidation of Ni(Pt)Si by molecular vs. atomic oxygen

X-ray photoelectron spectroscopy (XPS) has been used to characterize the oxidation of a clean Ni(Pt)Si surface under two distinct conditions: exposure to a mixed flux of atomic and molecular oxygen (O + O₂; PO+O₂ = 5 × 10⁻⁶ Torr) and pure molecular oxygen (O₂; PO₂ = 10⁻⁵ Torr) at ambient temperatures. Formation of the clean, stoichiometric (nickel monosilicide) phase under vacuum conditions results in the formation of a surface layer enriched in PtSi. Oxidation of this surface in the presence of atomic oxygen initially results in formation of a silicon oxide overlayer. At higher exposures, kinetically limited oxidation of Pt results in Pt silicate formation. No passivation of oxygen uptake of the sample is observed for total O + O₂ exposure <8 × 10⁴ L, at which point the average oxide/silicate overlayer thickness is 23 (3) Å (uncertainty in the last digit in parentheses). In contrast, exposure of the clean Ni(Pt)Si surface to molecular oxygen only (maximum exposure: 5 × 10⁵ L) results in slow growth of a silicon oxide overlayer, without silicate formation, and eventual passivation at a total average oxide thickness of 8(1) Å, compared to a oxide average thickness of 17(2) Å (no silicate formation) for the as-received sample (i.e., exposed to ambient.) The aggressive silicon oxidation by atomic oxygen, results in Ni-rich silicide formation in the substrate and the kinetically limited oxidation of the Pt.     

In situ XPS study of Pd(1 1 1) oxidation. Part 1: 2D oxide formation in 10 mbar O2

The oxidation of the Pd(1 1 1) surface was studied by in situ XPS during heating and cooling in 3 × 10⁻³ mbar O₂. A number of adsorbed/dissolved oxygen species were identified by in situ XPS, such as the two dimensional surface oxide (Pd₅O₄), the supersaturated O_ads layer, dissolved oxygen and the R 12.2° surface structure.Exposure of the Pd(1 1 1) single crystal to 3 × 10⁻³ mbar O₂ at 425 K led to formation of the 2D oxide phase, which was in equilibrium with a supersaturated O_ads layer. The supersaturated O_ads layer was characterized by the O 1s core level peak at 530.37 eV. The 2D oxide, Pd₅O₄, was characterized by two O 1s components at 528.92 eV and 529.52 eV and by two oxygen-induced Pd 3d_5/2 components at 335.5 eV and 336.24 eV. During heating in 3 × 10⁻³ mbar O₂ the supersaturated O_ads layer disappeared whereas the fraction of the surface covered with the 2D oxide grew. The surface was completely covered with the 2D oxide between 600 K and 655 K. Depth profiling by photon energy variation confirmed the surface nature of the 2D oxide. The 2D oxide decomposed completely above 717 K. Diffusion of oxygen in the palladium bulk occurred at these temperatures. A substantial oxygen signal assigned to the dissolved species was detected even at 923 K. The dissolved oxygen was characterised by the O 1s core level peak at 528.98 eV. The “bulk” nature of the dissolved oxygen species was verified by depth profiling.During cooling in 3 × 10⁻³ mbar O₂, the oxidised Pd²⁺ species appeared at 788 K whereas the 2D oxide decomposed at 717 K during heating. The surface oxidised states exhibited an inverse hysteresis. The oxidised palladium state observed during cooling was assigned to a new oxide phase, probably the R 12.2° structure.     

Studies on surface graft polymerization of acrylic acid onto PTFE film by remote argon plasma initiation

The graft polymerization of acrylic acid (AAc) was carried out onto poly(tetrafluoroethylene) (PTFE) films that had been pretreated with remote argon plasma and subsequently exposed to oxygen to create peroxides. Peroxides are known to be the species responsible for initiating the graft polymerization when PTFE reacts with AAc. We chose different parameters of remote plasma treatment to get the optimum condition for introducing maximum peroxides (2.87 × 10⁻¹¹ mol/cm²) on the surface. The influence of grafted reaction conditions on the grafting degree was investigated. The maximum grafting degree was 25.2 μg/cm². The surface microstructures and compositions of the AAc grafted PTFE film were characterized with the water contact angle meter, Fourier-transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). Contact angle measurements revealed that the water contact angle decreased from 108° to 41° and the surface free energy increased from 22.1 × 10⁻⁵ to 62.1 × 10⁻⁵ N cm⁻¹ by the grafting of the AAc chains. The hydrophilicity of the PTFE film surface was greatly enhanced. The time-dependent activity of the grafted surface was better than that of the plasma treated film.     

Study on the surface of fluorosilicone acrylate RGP contact lens treated by low-temperature nitrogen plasma

In order to improve the surface hydrophilicity of fluorosilicone acrylate rigid gas permeable (RGP) contact lens, low temperature nitrogen plasma was used to modify the lens surface. Effects of plasma conditions on the surface structures and properties were investigated. Results indicated that the surface hydrophilicity of RGP contact lens was significantly improved after treatment. X-ray photoelectron spectroscopy (XPS) results showed that the nitrogen element was successfully incorporated into the surface. Furthermore, some new bonds such as NCO, F⁻ and silicate were formed on the lens surface after nitrogen plasma treatment, which could result in the improvement of the surface hydrophilicity. Scanning electronic microscope (SEM) results indicated that nitrogen plasma with moderate power could make the surface smoother in some degree, while plasma with higher power could etch the surface.     

Isopropyl alcohol plasma modification of polystyrene surfaces to influence cell attachment behaviour

An isopropyl alcohol plasma has been used to modify polystyrene surfaces by the deposition of a hydrophilic thin film. The films have been characterised by X-ray photoelectron spectroscopy, atomic force microscopy and water contact angle measurements. These studies show the oxygen content of the modified surfaces increases with treatment time up to ∼10 at.% after 600 s. Monochromated XPS results show the surface oxygen to be in the form of carbonyl and alcohol/ether groups with a complete absence of carboxyl species. The suitability of the modified surfaces for cell culture was assessed by the growth of transformed human fibroblast cells (1BR.3N) in the presence of serum proteins which made up ∼10% (v/v) of the culture media. Plasma treatment times >60 s were found to result in cell attachment and proliferation rates comparable to tissue culture polystyrene which has a similar total surface oxygen concentration with the addition of a carboxyl group functionality. A simple chemical patterning technique was used to produce chemically heterogeneous surfaces for spatially resolved cell attachment studies. 1BR.3N cells were found to attach preferentially to the areas exposed to the plasma which were more hydrophilic than the untreated regions.     

The adsorption and reaction of H2O on clean and oxygen covered Ag(110)

The adsorption and reaction of water on clean and oxygen covered Ag(110) surfaces has been studied with high resolution electron energy loss (EELS), temperature programmed desorption (TPD), and X-ray photoelectron (XPS) spectroscopy. Non-dissociative adsorption of water was observed on both surfaces at 100 K. The vibrational spectra of these adsorbates at 100 K compared favorably to infrared absorption spectra of ice Ih. Both surfaces exhibited a desorption state at 170 K representative of multilayer H₂O desorption. Desorption states due to hydrogen-bonded and non-hydrogen-bonded water molecules at 200 and 240 K, respectively, were observed from the surface predosed with oxygen. EEL spectra of the 240 K state showed features at 550 and 840 cm^?1 which were assigned to restricted rotations of the adsorbed molecule. The reaction of adsorbed H₂O with pre-adsorbed oxygen to produce adsorbed hydroxyl groups was observed by EELS in the temperature range 205 to 255 K. The adsorbed hydroxyl groups recombined at 320 K to yield both a TPD water peak at 320 K and adsorbed atomic oxygen. XPS results indicated that water reacted completely with adsorbed oxygen to form OH with no residual atomic oxygen. Solvation between hydrogen-bonded H₂O molecules and hydroxyl groups is proposed to account for the results of this work and earlier work showing complete isotopic exchange between H₂¹⁶O_(a) and ¹⁸O_(a).     

Low temperature adsorption of oxygen on reduced V2O3(0 0 0 1) surfaces

Well ordered V₂O₃(0 0 0 1) films were prepared on Au(1 1 1) and W(1 1 0) substrates. These films are terminated by a layer of vanadyl groups under typical UHV conditions. Reduction by electron bombardment may remove the oxygen atoms of the vanadyl layer, leading to a surface terminated by vanadium atoms. The interaction of oxygen with the reduced V₂O₃(0 0 0 1) surface has been studied in the temperature range from 80 to 610 K. Thermal desorption spectroscopy (TDS), infrared reflection absorption spectroscopy (IRAS), high resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) were used to study the adsorbed oxygen species. Low temperature adsorption of oxygen on reduced V₂O₃(0 0 0 1) occurs both dissociatively and molecularly. At 90 K a negatively charged molecular oxygen species is observed. Upon annealing the adsorbed oxygen species dissociates, re-oxidizing the reduced surface by the formation of vanadyl species. Density functional theory was employed to calculate the structure and the vibrational frequencies of the O₂ species on the surface. Using both cluster and periodic models, the surface species could be identified as η²-peroxo () lying flat on surface, bonded to the surface vanadium atoms. Although the O-O vibrational normal mode involves motions almost parallel to the surface, it can be detected by infrared spectroscopy because it is connected with a change of the dipole moment perpendicular to the surface.     

Synchrotron radiation photoelectron spectroscopy and near-edge X-ray absorption fine structure study on oxidative etching of diamond-like carbon films by hyperthermal atomic oxygen

Surface structural changes of a hydrogenated diamond-like carbon (DLC) film exposed to a hyperthermal atomic oxygen beam were investigated by Rutherford backscattering spectroscopy (RBS), synchrotron radiation photoelectron spectroscopy (SR-PES), and near-edge X-ray absorption fine structure (NEXAFS). It was confirmed that the DLC surface was oxidized and etched by high-energy collisions of atomic oxygen. RBS and real-time mass-loss data showed a linear relationship between etching and atomic oxygen fluence. SR-PES data suggested that the oxide layer was restricted to the topmost surface of the DLC film. NEXAFS data were interpreted to mean that the sp² structure at the DLC surface was selectively etched by collisions with hyperthermal atomic oxygen, and an sp³-rich region remained at the topmost DLC surface. The formation of an sp³-rich layer at the DLC surface led to surface roughening and a reduced erosion yield relative to the pristine DLC surface.     

The surface chemistry resulting from low-pressure plasma treatment of polystyrene: The effect of residual vessel bound oxygen

The surface chemistry of plasma treated polystyrene samples has been studied in a specially designed low-pressure argon discharge system incorporating in situ XPS analysis. By using an electrostatic grid biasing technique, the plasma source can also be used in a mode preventing ion interactions with the sample.The system, which utilizes a vacuum transfer chamber between plasma and XPS analysis has allowed us to differentiate between the level of oxygen incorporated at the polystyrene surface from residual gas during treatment and that from the exposure of the treated sample to the laboratory atmosphere. Using typical base pressures of about 5 × 10⁻³ Pa (4 × 10⁻⁵ Torr) the XPS results show that significant oxygen surface incorporation resulted from oxygen containing species in the plasma itself (i.e. water vapour with 2 × 10⁻³ Pa partial pressure). The surface concentration of O was measured at 7.6 at.%. Subsequent atmospheric exposure of the treated samples resulted in only a small increase (of 0.6 at.%) in oxygen incorporation in the form of acid anhydride functionalities.XPS measurements of PS samples exposed to plasmas with no ion-surface component (i.e. exposure from VUV, UV and excited neutral species only) showed no appreciable change in oxygen incorporation compared to those with low-energy ion bombardment from the plasma (<20 eV). Given the energetics of the remaining bombarding species, it indicates that VUV radiation may be chiefly responsible for the production of free radical sites in this discharge regime.     

The reactions of acetone with the surfaces of uranium dioxide single crystal and thin film

The reaction of acetone, as an example of a carbonyl compound, is studied over UO₂ (1 1 1) single crystal and thin film surfaces. Over the stoichiometric single crystal surface, acetone is molecularly and weakly adsorbed with a computed activation energy for desorption in the range of 95-65 kJ/mol with pre-exponential factors between 10¹¹ and 10¹³ s⁻¹. On the contrary, acetone reacts very strongly on the O-defected single crystal and thin film surfaces. In addition to total decomposition evidence of aldolization and cyclization reactions were seen. The thin film of UO₂ was studied by synchrotron light, providing high resolution photoelectron spectroscopy in the core level, and high sensitivity in the both the core and valence band regions. The U5f line was considerably enhanced at grazing angle when compared to that obtained at normal angle for the O-defected surface, showing that the surface is more reduced than the next layers. The U 4f lines indicated the presence of U cations in lower oxidation states than +4 for the O-defected surface. These lines were considerably attenuated upon adsorption of acetone, due to surface oxidation by CO bond dissociation. The reaction pathway for acetone on the O-defected surface is presented, and compared to that of the previously studied acetaldehyde molecule.     

Identification of adsorbed species at metal surfaces by electron energy loss spectroscopy (EELS)

Electron energy loss spectroscopy (EELS) is a surface analysis method for measuring vibrational spectra of adsorbed species on metal surfaces. This paper summarizes recent work on the study of bonding of simple adsorbates on metal surfaces, and the identification of new chemical intermediates in reactions between two or more species in the adsorbed monolayer. The spectra of atomic oxygen, di-oxygen, water and ammonia adsorbed on platinum, copper and silver are discussed with emphasis on identification of the adsorbed species and their orientations relative to the surface plane. Surface reactions between atomic oxygen and water, methanol and formic acid yield the new surface intermediates hydroxyl (OH), methoxy (CH₃O) and formate (HCOO), respectively, on copper and silver surfaces. Each species was identified by comparison of surface spectra with known infrared spectra and through the use of deuterium isotopic shifts. The ability to identify and distinguish between chemical species at surfaces with high sensitivity will allow direct correlation of low pressure UHV surface experiments with high pressure surface reactions on catalysts and liquid-solid interfaces.     

Surface modification of polyethylene terephthalate with albumin and gelatin for improvement of anticoagulation and endothelialization

The surfaces of polyethylene terephthalate (PET) were modified by oxygen plasma-induced and ultraviolet (UV)-assisted acrylic acid (AAc) grafting polymerization, and the carboxyl (COOH) groups on the PET surface was 5.29 × 10⁻⁹mol/cm². Then using the COOH as reacting sites, the molecules of gelatin and bovine serum albumin (BSA) were further co-immobilized on the PET surface. The modified PET surfaces were characterized by X-ray photoelectron spectroscopy (XPS) and surface chemical quantitative analysis. The results showed that the molecules of gelatin and albumin were immobilized on the PET surface. The concentration of gelatin on the gelatin-immobilized PET surface was 2.02 μg/cm². For the gelatin-immobilized PET surface, the human umbilical vein endothelial cells (HUVECs) culture attachment and proliferation ratios were improved, but the anticoagulation became worse proved by platelet adhesion test in vitro and the lactate dehydrogense (LDH) test. After further co-immobilization of albumin with gelatin biomolecules on the PET surface (PET-Gel-BSA), the percent of platelet adhesion in vitro decreased 28% than that on the gelatin-immobilized PET surface, and the cell density on the PET-Gel-BSA film (1.08 × 10⁵ cells/cm²) was significantly higher than that on the control PET surface. This investigation tries to find a method which can construct the anticoagulant surface before the endothelium formation and also accelerate the endothelialization of polymer surface.     

The 1-v″ bands progression of the BΣ → XΣ system of CO

The B²Σ⁺ → X²Σ⁺ (0-1, 2, 3, 4 progression) electronic transition of ¹²C¹⁷O⁺ was first observed and analyzed by Szajna and Ke¸pa [Spectrochim. Acta A 65 (2006) 1014-1020]. We have now extended our previous studies. The use of high resolution conventional spectroscopic techniques has allowed first rotational analysis of the 1-2, 1-3, 1-4 and 1-5 bands of the first negative system in the 37,000-43,000 cm⁻¹ spectral region. Approximately 500 transition wavenumbers were measured with an estimated accuracy of 0.005 cm⁻¹. The present data were combined with the previous measurements to yield an improved set of molecular constants for the B²Σ⁺(v′ = 0, 1) and X²Σ⁺(v″ = 1, 2, 3, 4, 5). The v′ = 1 and v″ = 5 vibrational levels were observed for the first time and the main molecular constants are (in cm⁻¹, one standard deviation in parentheses)

B2Σ+		X2Σ+
B1 = 1.710792(20)		B5 = 1.825694(23)
D1 = 7.799(15) × 10−6		D5 = 6.085(21) × 10−6
γ1 = 1.9491(37) × 10−2		γ5 = [8.381] × 10−3

Full-size table

     

Reactivity of 3-hexyne on oxygen modified Ru(0 0 1) surfaces: Observation of oxametallacycles by RAIRS

The chemical behaviour of 3-hexyne on oxygen modified Ru(0 0 1) surfaces has been analysed under ultrahigh-vacuum, using reflection-absorption infrared spectroscopy (RAIRS). The effects of oxygen coverage, 3-hexyne exposure and adsorption temperature were studied. Two modified Ru(0 0 1) surfaces were prepared: Ru(0 0 1)-(2 × 2)-O and Ru(0 0 1)-(2 × 1)-O that correspond to oxygen coverages (θ_O) of 0.25 and 0.5 ML, respectively. The striking result is the direct bonding to an O atom when the modified surfaces are exposed to a very low dose (0.2 L) of 3-hexyne at low temperature (100 K). For θ_O = 0.25 ML, an unsaturated oxametallacycle [Ru-O-C(C₂H₅)C(C₂H₅)-Ru] is proposed, identified by RAIRS for the first time, through the νCC and νCO modes. Further decomposition at 110 K yields smaller oxygenated intermediates, such as acetyl [μ₃-η²(C,O)-CH₃CO], co-adsorbed with a small amount of carbon monoxide and non-dissociated species. The temperature at which a fraction of molecules undergoes complete C-C and C-H bond breaking is thus much lower than on clean Ru(0 0 1). The ultimate decomposition product observed by RAIRS at 220 K is methylidyne [CH]. Another key observation was that the adsorption temperature is not determinant of the reaction route, contrarily to what occurs on clean Ru(0 0 1): even when 3- hexyne strikes the surface at a rather high temperature (220 K), the multiple bond does not break completely. For θ_O = 0.5 ML, a saturated oxametallacycle [Ru-O-CH(C₂H₅)-CH(C₂H₅)-Ru] is also proposed at 100 K, identified by the ν_asO-C-C (at 1043 cm⁻¹) and ν_sO-C-C (at 897 cm⁻¹) modes, showing that some decomposition with C-H bond breaking occurs. For this oxygen coverage, the reaction temperatures are lower, and the intermediate surface species are less stable.