Size-selected Au clusters deposited on SiO2/Si: Stability of clusters under ambient pressure and elevated temperatures

This study examined the oxidation and reduction behavior of mass-selected Au clusters consisting of 2-13 atoms deposited on silica. An atomic oxygen environment was used for the oxidation of Au. X-ray photoelectron spectroscopy (XPS) was used to identify Au(III) and Au(O). Au₅, Au₇ and Au₁₃ clusters deposited on the as-prepared SiO₂/Si substrates were highly inert towards oxidation, whereas the other clusters could be oxidized, i.e. the chemical property drastically changed with the number of atoms in a cluster. The size-selectivity in chemical reactivity remained unchanged upon air-exposure. The chemical properties of the deposited Au clusters were unchanged after annealing at 250 °C. Annealing at higher temperatures caused structural changes to the surface, as determined by the oxidation behavior. XPS of the deposited Au clusters upon annealing indicated charge transfer from Au to silica.     

Sputtering of neutral clusters from silver-gold alloys

Polycrystalline Ag, Ag₂₀Au₈₀, Ag₄₀Au₆₀, Ag₈₀Au₂₀ and Au samples were bombarded with 15 keV Ar⁺ at 60° incidence and the resulting secondary neutral yield distribution was studied by non-resonant laser postionisation mass spectrometry. Neutral clusters containing up to 21 atoms were observed for the targets. The yield of neutral clusters, Ag_mAu_n−m, containing n atoms, Y_n, was found to follow a power in n, i.e. Y_n ∝ n^−δ, where the exponent δ varied from 3.2 to 4.0. For a fixed n, the cluster yields showed a variation with number of gold atoms similar to that expected for a binomial distribution. In addition, the cluster compositions from the sputtered alloys were indicative of sputtering from a gold rich surface.     

Formation of neutral clusters during sputtering of gold

Polycrystalline Au was bombarded with 15 keV Ar⁺, and the resulting secondary neutral cluster yield distribution was measured by laser postionisation mass spectrometry. Neutral Au_n clusters containing up to 20 atoms were observed. The yield of Au_n clusters, Y_n, was found to follow a power in n, Y_n ∝ n^−3.4, but the yield of individual clusters depended on whether n was even or odd. This odd-even yield variation was caused by fragmentation of the cluster photoions. Simulation of photoion trajectories within the TOF spectrometer shows that the fragmentation dominantly occurs before the photoions enter the reflectron part of the spectrometer.     

Experimental g factor of hydrogenlike silicon-28

Using the first principles calculations, the mixed Au _n Zn _m ⁺ (n + m ?? 6) cluster cations and their monocarbonyls Au _n Zn _m CO⁺ have been investigated at the PW91 level. For the small Au _n Zn _m ⁺ , most ground-state isomers are planar structures. A significant odd-even oscillation of the highest occupied-lowest unoccupied molecular orbital energy gaps with the number of Au atoms is observed. Upon CO adsorption, the top site and C head-on adsorptions are most favorable in energy. Moreover, the optimized geometries indicate that the CO molecule prefers binding to Au atom of the Au _n Zn _m ⁺ clusters, which can be understood by the frontier molecular orbital theory in detail. From the theoretical calculations, the CO charge population, CO binding energy (BE) and the Gibbs free-energy change ??G generally decrease with the increase of the Zn content. It is found that the BE is highly related to the electron transfer between CO and the cluster cations. Furthermore, a linear correlation between ??G and the CO BE is found. The red shift in the CO stretching frequency is sensitive to the cluster size and composition. Our calculation suggests that CO reactive collision on Au₃Zn⁺ and Au₂Zn ₂ ⁺ may lead to the dissociation of the clusters with a Zn atom loss.     

Study of the structure and electronic state of thiolate-protected gold clusters by means of 197Au Mössbauer spectroscopy

We have investigated the structures and electronic states of a series of glutathionate-protected Au clusters, Au _n (SG) _m with n = 10 ? ～55, using ¹⁹⁷Au Mössbauer spectroscopy, which allows us to probe the local environment of the constituent Au atoms via isomer shift (IS) and quadrupole splitting (QS). The spectral profile abruptly changes on going from Au₂₂(SG)₁₇ to Au₂₅(SG)₁₈, then it smoothly changes to that of Au～₅₅(SG)_m. However, the spectral profile dramatically changes on going from Au～₅₅(SG)_m to the dodecanethiolate-protected Au cluster with average diameter of 2 nm. The ¹⁹⁷Au Mössbauer spectra of glutathionate-protected Au clusters and dodecanethiolate-protected Au clusters were successfully analyzed on the basis of the structure and electronic state of Au₂₅(SG)₁₈.     

Catalytically active gold clusters and nanoparticles for CO oxidation

Electronic states of gold nanoparticles in mordenite and their transformations under redox treatments have been studied by the methods of FTIR spectroscopy of adsorbed CO and diffuse reflectance UV-visible spectroscopy. Different states of ionic and metallic gold were detected in the zeolite channels and on the external surface of the zeolite - Au⁺ and Au³⁺ ions, charged clusters , and neutral nanoparticles Au_m. Catalytic tests of the samples revealed the existence of two types of active sites of gold in CO oxidation - gold clusters <2 nm (low-temperature activity) and gold nanoparticles (high temperature activity).     

Effect of alloying on the stabilities and catalytic properties of Pt–Au bimetallic subnanoclusters: a theoretical investigation

Density functional theory (DFT) has been applied to study the geometrical and electronic structures and the catalytic properties for NO oxidation of pure Pt and PtAu clusters. The calculated results suggest that Pt₁₀ clusters shows the most stable structure among the pure Pt _n (n = 2–13) clusters with the local maximum Δ₂ E value. The doping of Au atoms reduces the stability of the clusters, and Pt₆Au₄ cluster has the most stable structure among Pt_10?n Au _n (n = 1–7) clusters, due to the closest band centers between Pt and Au atoms (0.83 eV) and the obvious s–p resonance peaks near the Fermi level. Pt₆Au₄ cluster displays the strongest activation of O₂ molecules among Pt_10?n Au _n (n = 0–7) clusters, owing to the clear overlap between O 2p and Pt 6 s and Au 6 s near the Fermi level, and the more positive d band center than the others. The interaction between NO and metals changes slightly in NO/Pt_10-nAu_n (n = 2–7) systems, which is weaker than that in NO/Pt₉Au system, as a result of the decreasing resonance peaks of sp hybridization near the Fermi level. Compared to pure Pt₁₀ cluster, the lower energy barriers and larger reaction energies on Pt₆Au₄ cluster suggest a higher catalytic activity of PtAu cluster for the O₂ dissociation and NO oxidation reactions. Our study provides atomic-scale insights into the nature of the interfacial effect that determines NO oxidation on PtAu cluster catalysts.     

Electrical and chemical characteristics of nano-meter gold encapsulated in mesoporous and microporous channels and cages of FSM-16 and Y zeolites

The dc and ac conductivities as well as the dielectric constant () were measured for different zeolites encapsulated gold (AuCl₃) samples at different temperatures (300-500 K) and various frequencies (5 kHz-1 MHz). The conductivity was found to change in the order Au/FSM-27>Au/NaY>Au/FSM-47. Sorbed water contained inside zeolites assists greatly the proton mobility (zeolite protons) and the ion mobility (Na⁺ and Au⁺) and hence enhance the electric conduction in the temperature range 300-373 K. Raising the temperature over 373 K induces dehydration effect that assists the metallic gold formation and thus a dramatic loss in conductivity was revealed. The conduction mechanism was expected to be partially ionic and partially electronic. The IR study showed that the exposure of Au zeolites to CO gas produced a characteristic band of Au⁺-CO at 2180 cm⁻¹ that tends to decrease with temperatures and even vanishes at 376 K in favor of Au⁰-CO at 2128 cm⁻¹. Similarly, a phase transition at 338 K, that occurs in the range 300-376 K, was confirmed by DTA to further emphasize the temperature regions of either Au⁺ cations (338 K) or Au⁰ (376 K) formation.     

Dynamics of gold clusters on amorphous carbon films induced by annealing in a transmission electron microscope

The change of the size distribution of Au clusters induced by annealing was studied in situ by transmission electron microscopy. Starting from statistically distributed Au clusters on a thin amorphous carbon film, “islands” are formed within a few months storage at room temperature, which consist of Au clusters with sizes <4 nm embedded in a thin Au film. These islands cover originally areas with sizes around 25 × 70 nm². If the temperature is increased in the transmission electron microscope two different processes can be clearly distinguished that lead to the coarsening of the cluster size distribution: cluster coalescence and (contactless) Ostwald ripening. The degree and rate of the coarsening are found to depend on the underlying surface (Au film or amorphous carbon) and the exposure to the high-flux high-energy electron beam, which can be estimated to lead to high-temperature excursions in a cluster on a 10⁻¹² s time scale. The experimental findings are confirmed by Monte-Carlo simulations using the many-body Gupta potentials in order to calculate the Au/Au interaction. Moreover, the results of MC simulations suggest an electron-beam induced formation of a “quasi-two-dimensional gas” of small highly mobile Au species on the Au film, which promotes Ostwald ripening.     

Metal-CdZnTe contact and its annealing behaviors

The electrical properties of different metal-CdZnTe contacts by sputtering deposition method are investigated by current-voltage. The results show that Au is the most suitable electrical contact materials, which forms the nearly ideal Ohmic contact with high resistivity p-CdZnTe crystals. Ohmicity coefficient b is the closest to 1 after 10 min annealing at 333 K, which is analyzed by current-voltage characteristics. XPS analyses show that Au atoms diffuse into CdZnTe during annealing process and Cd and Te atoms diffuse into Au contact. Diffused Au atoms do not form any compound with any element in CdZnTe crystal. PL spectra results of Au deposition on CdZnTe crystals at 10 K show that the inter-diffused donors [Au]³⁺ recombine with acceptors [V_Cd]²⁻ during sputtering process. Meanwhile, the intensity of (D_complex) peak of with Au contact increases sharply in comparison with un-deposited CdZnTe crystal and donor [Au]³⁺ and can compensate Cd vacancy [V_Cd]²⁻ wholly.     

Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au_xH_yS_z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au_xH_yS_z (x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au_xH_yS_z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M−S+H)Na⁺, (M+H)Na⁺, AuMNa⁺, (M₂−S)Na⁺, and M₂Na⁺ are determined, and also in cationized forms with K⁺. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM₂ and Au₂M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au_xM_w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.     

Spectroscopic ellipsometry study of the dielectric response of Au-In and Ag-Sn thin-film couples

Optical properties and phase composition of In-Au and Sn-Ag ultra-thin films grown by sequential evaporating and co-depositing of metals in a vacuum were investigated combining X-ray diffraction and spectroscopic ellipsometry methods. The atomic concentration ratios of bilayer and co-deposited samples were the same, i.e. In(Sn):Au(Ag) = 1:2. The XRD patterns indicated creation of AuIn, AuIn₂, Au₃In₂, Au₉In₄ and Ag₃Sn intermetallic compounds at room temperature. The effective complex dielectric functions of the composite layers, , were determined from ellipsometric quantities Ψ and Δ measured in a photon energy range of 0.6-6.5 eV. The free-carrier parameters (unscreened plasma frequency and free-carrier damping) and optical resistivity were evaluated using a semiclassical Drude-Lorentz model of the effective dielectric function. There was noticed a distinct influence of phase composition and surface morphology on the optical constants and conductivity of the samples: ρ_op changed from approximately 15 μΩ cm to 37 μΩ cm for Ag-Sn structures, composed of β-Sn and Ag₃Sn phases, and from 21 μΩ cm to 83 μΩ cm for Au-In multiphase system. Lower resistivity demonstrated diffusive layers formed after deposition of an In(Sn) thin film on the noble metal underlayer.     

Mechanism and kinetics of the diffusion of gold in silicon

The diffusion of Au in Si is known to take place via the interchange of Au atoms between substitutional (Au _s ) and interstitial (Au _i ) sites. So far it has generally been believed that this interchange involves lattice vacancies (V) and that it occurs via the Frank-Turnbull mechanism V+Au _i ⇆Au _s . It is stated in the literature that this model explains the observation that the Au _s concentrationC _s ^m in the centre of Au-diffused Si wafers increases with timet according to . We show that this statement is incorrect, i.e., the Frank-Turnbull model cannot account for the law. Such a dependence is expected in the case of Si wafers with a sufficiently low density of internal sinks for self-interstitials if the Au _i −Au _s interchange is controlled by the so-called kick-out mechanism Au _i ⇆Au _s +1. Since this mechanism involves self-interstitials (I) the present result is in accordance with the fact that under high-temperature equilibrium conditions the dominating intrinsic point defects in Si are self-interstitials and not vacancies as in Ge or metals.     

Formation of Sim and SimCn clusters by C60 sputtering of Si

The secondary ion mass spectrum of silicon sputtered by high energy C₆₀⁺ ions in sputter equilibrium is found to be dominated by Si clusters and we report the relative yields of Si_m⁺ (1 ≤ m ≤ 15) and various Si_mC_n⁺ clusters (1 ≤ m ≤ 11 for n = 1; 1 ≤ m ≤ 6 for n = 2; 1 ≤ m ≤ 4 for n = 3). The yields of Si_m⁺ clusters up to Si₇⁺ are significant (between 0.1 and 0.6 of the Si⁺ yield) with even numbered clusters Si₄⁺ and Si₆⁺ having the highest probability of formation. The abundances of cluster ions between Si₈⁺ and Si₁₁⁺ are still significant (>1% relative to Si⁺) but drop by a factor of ∼100 between Si₁₁⁺ and Si₁₃⁺. The probability of formation of clusters Si₁₃⁺-Si₁₅⁺ is approximately constant at ∼5 × 10⁻⁴ relative to Si⁺ and rising a little for Si₁₅⁺, but clusters beyond Si₁₅ are not detected (Si_m≥16⁺/Si⁺ < 1 × 10⁻⁴). The probability of formation of Si_m⁺ and Si_mC_n⁺ clusters depends only very weakly on the C₆₀⁺ primary ion energy between 13.5 keV and 37.5 keV. The behaviour of Si_m⁺ and Si_mC_n⁺ cluster ions was also investigated for impacts onto a fresh Si surface to study the effects that saturation of the surface with C₆₀⁺ in reaching sputter equilibrium may have had on the measured abundances. By comparison, there are very minor amounts of pure Si_m⁺ clusters produced during C₆₀⁺ sputtering of silica (SiO₂) and various silicate minerals. The abundances for clusters heavier than Si₂⁺ are very small compared to the case where Si is the target.The data reported here suggest that Si_m⁺ and Si_mC_n⁺ cluster abundances may be consistent in a qualitative way with theoretical modelling by others which predicts each carbon atom to bind with 3-4 Si atoms in the sample. This experimental data may now be used to improve theoretical modelling.     

Yields and ionization probabilities of sputtered Inn particles under atomic and polyatomic Aum ion bombardment

The emission of neutral and charged atoms and clusters from a polycrystalline indium surface under bombardment with 5 and 10 keV Au, Au₂, Au₃ and Au₅ projectiles was investigated. Single photon laser postionization was utilized for the detection of sputtered neutral particles. Secondary ions were detected without the laser under otherwise exactly the same experimental conditions. The relative cluster yields were found to be enhanced under polyatomic projectile bombardment, more so the larger the number of atoms in the sputtered cluster. The ionization probability strongly increases with increasing cluster size, but is essentially independent of the projectile impact energy. At a fixed impact energy, the ionization probability of sputtered monomers was found to decrease with increasing number of constituent gold atoms per projectile, but there was no detectable effect for sputtered dimers and larger clusters.     

Self-regulated Ni cluster formation on the TiO2(1 1 0) terrace studied using scanning tunneling microscopy

We have studied the growth mode and morphology of Ni clusters on a TiO₂(1 1 0) surface with a wide terrace using scanning tunneling microscopy (STM) at a low coverage (less than 3 atoms nm⁻²). The Ni clusters are formed on the terrace at the low coverage of 0.2 atoms nm⁻². Their average dimensions are constant in three directions up to 1 atoms nm⁻². The Ni clusters have an oval shape with average sizes of 1.8 nm (along [0 0 1]) × 1.4 nm (along (in the [1 1 0] directions). Above the coverage of 1.0 atoms nm⁻², an increase in the cluster height occurs, retaining an almost constant lateral size. It is proposed that the interaction of the Ni cluster and the support surface regulates the Ni cluster size.     

Deformation of slow liquid and solid clusters upon deposition: A molecular-dynamics study of Al cluster impact on an Al surface

Using molecular-dynamics simulation, we investigate the self-deposition of Al_n clusters (n < 4000) on an Al substrate at velocities below the velocity of sound. Both cold crystalline and hot liquid clusters are studied. We examine the cluster deformation after impact on the surface, which we quantify by its height and base radius. At a given cluster velocity, the shape of deposited crystalline clusters is rather independent of the cluster size; only at small cluster sizes, n ? 40, the clusters are less strongly deformed. With increasing cluster size, liquid clusters are more strongly deformed than crystalline clusters. Faster projectiles become more strongly flattened by the deposition process. Even clusters depositing with vanishing velocity show a finite deformation, which is considerable for smaller clusters. At large cluster speed, clusters penetrate deeper into the (1 0 0) surface than into the (1 1 1) surface and also deform more strongly.     

Gold chloride cluster ions generated by vacuum laser ablation

In this work, a simple way for study the possibility of formation a vapor cluster species of tetrachloroauric acid (HAuCl₄), using the laser ablation in the absence of a buffer or reactive atmosphere, and without a postablation supersonic expansion on a commercial matrix assisted laser desorption/ionization time-of-flight mass spectrometer, is reported. Tetrachloroauric acid is known as precursor for the synthesis of gold nanostructures and the complex salts; therefore it is an important task to discover and quantify the species arising from HAuCl₄, in order to understand their role in the gold assisted reactions. Mass spectrum of HAuCl₄ in a reflector negative-ion mode contains the hydrated mono- and dinuclear gold clusters in the m/z range 286–436, and gold chloride clusters in the m/z range 447–795. In the first part of spectrum, m/z range 286–436, the hydrated gold cluster species of type Au _n ^? (H₂O)_m (n?=?1–2; m?=?1, 2, 5, 7, 8) and [Au_n(OH)_k]^?(H₂O)_m (n?=?1–2; k?=?1–2; m?=?1, 4–8) were found. Besides that, there are gold chloride clusters with general formula [AuH_r(HCl)₂]^?(H₂O)_m (m?=?1–5; 8–9; r?=?0–2) in this part of spectrum. In the second part of spectrum, the m/z range 447–795, only gold chloride clusters were obtained. Their general formulae can be written as [AuCl_t(HCl)_v]^?(H₂O)_m (t?=?1–4; v?=?5–8; m?=?2–4, 6–8) and [Au_n(HCl)_v]^?(H₂O)_m (n?=?1–2, v?=?4–5, m?=?1–2, 5, 7). The analysis of concentration effects on the LDI mass spectra of gold clusters reveals that the relative intensities of signals for the mono- and dinuclear Au clusters increase with decreasing the concentration of water HAuCl₄ solutions.     

NMR-ON on196,197m,198,198m,200mAu in Fe and Ni

The zero-field hyperfine splitting frequencies of a series of Au isotopes in Fe and Ni have been determined with nuclear magnetic resonance on oriented nuclei. The results are:. For¹⁹⁸Au(2^–) in Fe the quadrupole splitting could be resolved. The results are ¦g_NB_HF/h|=259.48 (3) MHz and e²qp/h=–2.08(4) MHz. Our measurements show that most hyperfine splittings published on these isotopes have been incorrect. The quadrupole splitting of¹⁹⁸AuFe disagrees in magnitudeand sign from the value reported by single-passage NMR on oriented nuclei. The following nuclear quantities are deduced: (^197mAu,11/2^–)=5.98(9) _N; (^198mAu, 12^–)=5.85(9) _N; (^200mAu, 12^–)=5.90(9) _N; Q(¹⁹⁸Au,2^–)/Q(¹⁹⁹Au, 3/2⁺)=1.37(3). Our measurements show further that the non-contact hyperfine field for Au in Ni is smaller than assumed previously, and that the magnetic hyperfine splitting frequency of¹⁹⁷AuFe known from NMR is inconsistent with the magnetic hyperfine splitting frequencies of^{198, 199}AuFe.     

Structural properties and reactivity of bimetallic silver-gold clusters

Bimetallic silver-gold clusters are well suited to study changes in metallic versus ionic properties involving charge transfer as a function of the size and the composition. We present structures, ionization potentials (IP) and vertical detachment energies (VDE) for neutral and charged bimetallic Au_nAg_m ( 2(n + m)5) clusters obtained from density functional level of theory. In the stable structures of these clusters Au atoms assume positions which favor charge transfer from Ag atoms. In clusters with equal numbers of hetero atoms (n = m = 1- 4) heteronuclear bonding is preferred to homonuclear bonding, giving rise to large values of ionization potentials. For larger clusters (n=m=5, 10) stable structures do not favor neither hetero bonding nor segregation into the single components, although they exhibit more metallic than ionic features. This remains valid also for Au₈Ag₁₂ cluster characterized by strong charge transfer to gold subunit. The influence of doping of pure gold clusters with silver atoms on VDE and IP values is discussed in context of their reactivity towards O₂ and CO molecules. As a starting point we consider reactivity towards CO and O₂ molecules on the example of AgAu^- dimer. The results show that the catalytic cycle can be fullfilled.