Electrodeposition of Al in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ionic liquids: in situ STM and EQCM studies

In the present paper, the electrodeposition of Al on flame-annealed Au(111) and polycrystalline Au substrates in two air- and water-stable ionic liquids namely, 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py(1,4)]Tf(2)N, and 1-ethyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide, [EMIm]Tf(2)N, has been investigated by in situ scanning tunneling microscopy (STM), electrochemical quartz crystal microbalance (EQCM), and cyclic voltammetry. The cyclic voltammogram of aluminum deposition and stripping on Au(111) in the upper phase of the biphasic mixture of AlCl(3)/[EMIm]Tf(2)N at room temperature (25 degrees C) shows that the electrodeposition process is completely reversible as also evidenced by in situ STM and EQCM studies. Additionally, a cathodic peak at an electrode potential of about 0.55 V vs Al/Al(III) is correlated to the aluminum UPD process that was evidenced by in situ STM. A surface alloying of Al with Au at the early stage of deposition occurs. It has been found that the Au(111) surface is subject to a restructuring/reconstruction in the upper phase of the biphasic mixture of AlCl(3)/[Py(1,4)]Tf(2)N at room temperature (25 degrees C) and that the deposition is not fully reversible. Furthermore, the underpotential deposition of Al in [Py(1,4)]Tf(2)N is not as clear as in [EMIm]Tf(2)N. The frequency shift in the EQCM experiments in [Py(1,4)]Tf(2)N shows a surprising result as an increase in frequency and a decrease in damping with bulk aluminum deposition at potentials more negative than -1.8 V was observed at room temperature. However, at 100 degrees C there is a frequency decrease with ongoing Al deposition. At -2.0 V vs Al/Al(III), a bulk aluminum deposition sets in.     

Raman and FTIR Spectroscopic Studies of 1‐Ethyl‐3‐methylimidazolium Trifluoromethylsulfonate,its Mixtures with Water and the Solvation of Zinc Ions

In this paper we report on the interactions of the ionic liquid 1‐ethyl‐3‐methylimidazolium trifluoromethylsulfonate ([EMIm]TfO) with water and the solvation of zinc ions in neat [EMIm]TfO and [EMIm]TfO–water mixtures investigated by FTIR and Raman spectroscopy. The structures and physicochemical properties of the [EMIm]TfO–water mixtures are strongly dependent on the interaction between cations, anions, and water. The structure was changed from ionic‐liquid‐like to water‐like solutions upon addition of water. In addition, zinc salts can precipitate in 0.2 M Zn(TfO)₂/[EMIm]TfO upon addition of 10 % (v/v) water, presumably as a result of polarity change of the solution. The average coordination number of TfO^? per zinc ion calculated from Raman spectra is 3.8 in neat [EMIm]TfO, indicating that [Zn(TfO)₄]^2?, and [Zn(TfO)₃]^? complexes are present in the solution. However, in the presence of water, water interacts preferentially with the zinc ions, leading to aqueous zinc species. The solvation of zinc ions in 1‐butyl‐1‐methylpyrrolidinium trifluoromethylsulfonate ([Py_1,4]TfO) was also investigated. In [Py_1,4]TfO, there are, on average, 4.5 TfO^? anions coordinating each zinc ion, corresponding to the weak interaction between [Py_1,4]⁺ cations and TfO^? anions. The species present in [Py_1,4]TfO are likely a mixture of [Zn(TfO)₄]^2? and [Zn(TfO)₅]^3?.     

Electrodeposition of silicon from three different ionic liquids: possible influence of the anion on the deposition process

The electrodeposition of silicon was investigated from three different ionic liquids with the cation 1-butyl-1-methylpyrrolidinium ([Py_1,4]⁺) and three different anions, namely, trifluoromethylsulfonate (TfO^?), bis(trifluoromethylsulfonyl)amide (TFSA^?) and tris(pentafluoroethyl)-trifluorophosphate (FAP^?) at room temperature and at 100 °C, respectively. The electrodeposition was performed on gold and on copper substrates. Cyclic voltammetry was used to evaluate the possible influence of anions on the deposition process. In situ STM studies were also carried out to examine the interfacial behaviour of the SiCl₄/[Py_1,4]TFSA and SiCl₄/[Py_1,4]FAP on Au(111) at room temperature. In situ STM measurements revealed that an underpotential deposition of Si in [Py_1,4]FAP occurred on Au (111) at ~ -0.5 V (vs. Fc/Fc⁺). In comparison, only adsorption of ionic liquid and gold surface reconstruction was found to occur in the potential regime between -0.3 and ?1.8 V (vs. Fc/Fc⁺), respectively, in the case of [Py_1,4]TFSA. In situ STM investigations reveal an effect of the anion on the interfacial processes. In situ I/U tunnelling spectroscopy shows that the band gap of the electrodeposits is ~1.1 eV, indicating that semiconducting silicon has been electrodeposited. Potentiostatic electrolysis was performed to deposit Si from the employed electrolytes at room temperature and at 100 °C. The deposits were characterised using scanning electron microscopy and X-ray diffraction. Thin films of Si could be obtained from the employed ionic liquids and the quality of the deposits was significantly improved at 100 °C.     

An in situ STM and DTS study of the extremely pure [EMIM]FAP/Au(111) interface

Herein the structure of the interfacial layer between the air- and water-stable ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM]FAP) and Au(111) is investigated using in situ scanning tunneling microscopy (STM), distance tunneling spectroscopy (DTS) and cyclic voltammetry (CV) measurements. The in situ STM measurements reveal that structured interfacial layers can be probed in both cathodic and anodic regimes at the IL/Au(111) interface. The structure of these layers is dependent on the applied electrode potential, the number of subsequent STM scans and the scan rate. Furthermore, first DTS results show that the tunneling barrier during the 1st STM scan does not seem to change significantly in the cathodic potential regime between the ocp (-0.2 V) and -2.0 V.     

Electrodeposition of nanocrystalline aluminium, copper, and copper–aluminium alloys from 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate ionic liquid

In this paper, we show that nanocrystalline aluminium, copper, and copper–aluminium alloys can be electrodeposited from the ionic liquid 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate, [Py_1,4]TfO. Furthermore, Al deposition was studied in 1-ethyl-3-methylimidazolium trifluoromethylsulfonate, [EMIm]TfO for comparison. The two employed ionic liquids exhibit different concentration-dependent phase behaviour with AlCl₃. This study comprises cyclic voltammetry, potentiostatic electrolysis, scanning electron microscopy, X-ray diffraction, atomic absorption spectroscopy, and inductively coupled plasma optical emission spectroscopy. Thick (in micrometre regime) and uniform layers of aluminium deposits were obtained from 2.75?M AlCl₃ in [Py_1,4]TfO at 100?°C. The average crystallite size of aluminium was found to be around 40 to 50?nm. However, a coarse and cubic-shaped Al deposit with crystal sizes in the micrometre regime was obtained from [EMIm]TfO. Electrodeposition of copper was investigated in [Py_1,4]TfO-containing Cu(TfO)₂ at 100?°C. The average grain size of the copper deposit obtained from the electrolysis is around 20 to 40?nm. Electrodeposition of copper–aluminium alloys was successful in the same ionic liquid at 100?°C. Thick layers of copper–aluminium alloys were obtained from the employed ionic liquid. XRD analysis of the obtained deposits from electrolysis experiments revealed that Cu₃Al alloy was formed. SEM analysis indicated that the nanocrystalline copper–aluminium deposits have an average grain size of 60 to 70?nm.     

Two-dimensional connective nanostructures of electrodeposited Zn on Au (111) induced by spinodal decomposition

Phase formation of surface alloying by spinodal decomposition has been studied at an electrified interface. For this aim Zn was electrodeposited on Au(111) from the ionic liquid AlCl(3)-MBIC (58:42) containing 1 mM Zn(II) at different potentials in the underpotential range corresponding to submonolayer up to monolayer coverage. Structure evolution was observed by in situ electrochemical scanning tunneling microscopy (STM) at different times after starting the deposition via potential jumps and at temperatures of 298 and 323 K. Spinodal or labyrinth two-dimensional structures predominate at middle coverage, both in deposition and in dissolution experiments. They are characterized by a length scale of typically 5 nm which has been determined from the power spectral density of STM images. Structure formation and surface alloying are governed by slow kinetics with a rate constant k with activation energy of 120 meV and preexponential factor of 0.17 s(-1). The evolution of the structural features is described by a continuum model and is found to be in good agreement with the STM observations. From the experimental and model calculation results we conclude that the two-dimensional phase formation in the Zn on Au(111) system is dominated by surface alloying. The phase separation of a Zn-rich and a Zn-Au alloy phase is governed by two-dimensional spinodal decomposition.     

The structure, growth and reactivity of electrodeposited Ru/Au(111) surfaces

In order to elucidate electronic effects on the oxidation of CO on small Ru clusters, we investigated this reaction on well defined Ru/Au(111) model systems via parallel in-situ STM studies of the structure and electrochemical deposition of Ru on Au(111) in H₂SO₄ solution and cyclic voltammetry of CO monolayer oxidation on these surfaces. The Ru deposit consists of nanoscale islands, which coalesce with increasing coverage. The Ru saturation coverage depends on the deposition potential, resulting in Ru submonolayer (>0.1 V), (defective) monolayer (≥−0.1 V), and multilayer films (<−0.1 V). At potentials >0.6 V irreversible formation of Ru oxide/hydroxide species is observed, which can be partly reduced in the range 0.4 to 0.0 V. CO stripping commences at ≈0.1 V and occurs over a broad potential range. From the stripping charge a local CO coverage on the Ru monolayer islands of 0.7 ML was estimated. The observed influence of the morphology of the Ru deposit on the CO stripping voltammetry is explained by (local) variations in the CO adsorption energy due to electronic modifications of the Ru film.     

Electrodeposition of Al,Zn, and Pt on silver-coated textile fibres from ionic liquids

In the present paper, we report on the electrodeposition of aluminium, zinc and platinum on silver-coated textile fibres from ionic liquids. For electrodeposition of Al, the 60:40 mol% mixture of AlCl₃/1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1.7 M AlCl₃ in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py_1,4]TFSA) were employed. It was observed that microcrystalline aluminium was electrodeposited on the textile fibres in 60:40 mol% AlCl₃/[EMIm]Cl. The deposited Al layers either on single fibres or on textile assemblies are well adherent and uniform. An adherent, homogeneous and nanocrystalline Al layer was obtained on the silver-coated textile samples from 1.7 M AlCl₃/[Py_1,4]TFSA at 75 °C. The obtained Al layers from 60:40 mol% AlCl₃/[EMIm]Cl on the textile fibres exhibit a good corrosion resistance in an aqueous iodide/iodine electrolyte. Furthermore, we obtain Al microtubes from the investigated ionic liquids after dissolving the textile fibres. In addition, zinc electrodeposition was carried out on the textile samples from 60:40 mol% ZnCl₂/[EMIm]Cl at 80 °C. The electrodeposition of platinum on the textiles was done from 50 mM PtCl₂ in 1-butyl-1-methylpyrrolidinium dicyanamide ([Py_1,4]DCA).     

Electrodeposition and stripping of zinc from an ionic liquid polymer gel electrolyte for rechargeable zinc-based batteries

In this paper, we report on zinc deposition and stripping in an ionic liquid polymer gel electrolyte on gold and copper substrates, respectively. The ionic liquid-based polymer gel electrolyte is prepared by combining the ionic liquid 1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate ([Py_1,4]TfO), with Zn(TfO)₂ and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP). The ionic liquid polymer gel electrolyte exhibits good conductivity (2.2 mS cm^?1) and good mechanical stability. Zinc deposition and stripping in the ionic liquid polymer gel electrolyte were studied by cyclic voltammetry, potentiostatic, and galvanostatic cycling (charging/discharging) experiments. The gel electrolyte exhibits a promising electrochemical stability and allows a quasi-reversible zinc deposition/stripping. The morphology of the zinc deposits after 10 cycles of zinc deposition/stripping is compact and dense, and deposits without any dendrite formation can be obtained. The quasi-reversibility of the electrochemical deposition/stripping of zinc in this ionic liquid polymer gel electrolyte is of interest for rechargeable zinc-based batteries.     

STM and voltammetric studies on the structure of a 4-pyridinethiolate monolayer chemisorbed on Au(100)-(1×1) surface

The structure for a 4-pyridinethiolate monolayer chemisorbed on the Au(100)-(1×1) single crystal surface was characterized by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). In situ STM observation showed a well-ordered p(√2 R 45°×5 R 53.1°) structure (abbreviated as √2×5) for the surface modified with either 4-pyridinethiol (4-PySH) or bis(4-pyridyl)disulfide (4,4′-PySSPy) in a 0.05 M HClO₄ solution. On the Au(100)-(1×1) surface, 4-PySH molecules formed a dimer structure with the S–S bond length of about 2.4 nm. The observed dimer structure is similar to that previously reported on the Au(111) surface, and the orientation of the pyridine ring is mostly perpendicular to the surface normal. However, the adsorbed molecules were more densely packed (√3/√2 times) on the Au(100) surface than on the Au(111) surface. The surface excess was estimated to be 5.8 (±0.2)×10⁻¹⁰ mol cm⁻² based on the voltammetric charge for the reductive desorption. This value is in good agreement with that (5.7×10⁻¹⁰ mol cm⁻²) calculated from the parallelogrammic (√2×5) unit cell. The Au(100)-(1×1) surface modified with 4-PySH gave a well-defined electrochemical response of cytochrome c.     

Pb deposition on I-coated Au(111). UHV-EC and EC-STM studies

This article concerns the growth of an atomic layer of Pb on the Au(111)( radical3 x radical3)R30 degrees -I structure. The importance of this study lies in the use of Pb underpotential deposition (UPD) as a sacrificial layer in surface-limited redox replacement (SLRR). SLRR reactions are being applied in the formation of metal nanofilms via electrochemical atomic layer deposition (ALD). Pb UPD is a surface-limited reaction, and if it is placed in a solution of ions of a more noble metal, redox replacement can occur, but limited by the amount of Pb present. Pb UPD is a candidate for use as a sacrificial layer for replacement by any more noble element. It has been used by this group for both Cu and Pt nanofilm formation using electrochemical ALD. The I atom layer was intended to facilitate electrochemical annealing during nanofilm growth. Two distinctly different Pb atomic layer structures are reported, studied using in situ scanning tunneling microscopy (STM) with an electrochemical flow cell and ultrahigh vacuum surface analysis combined directly with electrochemical reactions (UHV-EC). Starting with the initial Au(111)( radical3 x radical3)R30 degrees -I, 1/3 monolayer of I on the Au(111) surface, Pb deposition began at approximately 0.1 V. The first Pb UPD structure was observed just below -0.2 V and displayed a (2 x radical3)-rect unit cell, for a structure composed of 1/4 monolayer each of Pb and I. The I atoms fit in Pb 4-fold sites, on the Au(111) surface. The structure was present in domains rotated by 120 degrees. Deposition to -0.4 V resulted in complete loss of the I atoms and formation of a Pb monolayer on the Au(111), which produced a Moiré pattern, due to the Pb and Au lattice mismatch. These structures represent two well-defined starting points for the growth of nanofilms of other more noble elements. It is apparent from these studies that the adsorption of I- on Pb is weak, and it will rinse away. If Pb is used as a sacrificial metal in an electrochemical ALD cycle and adsorbed I atoms are employed for electrochemical annealing, I atoms will need to be applied each cycle.     

In situ STM study of Au(111)/Os bimetallic surfaces: spontaneous deposition and electrochemical dissolution

We provide an electrochemical and structural characterization by in situ STM of Au(111)/Os electrodes prepared by spontaneous deposition of Os on Au(111). Surfaces with Os coverage values up to the saturation coverage were examined, from 10%. Using comparisons to previous work on Au(111)/Ru, Pt(111)/Ru, and Pt(111)/Os, we find that we may now generalize that Os deposits spontaneously faster than Ru and has a greater tendency to form 3-D structures. Additionally, the Au(111) substrate shows preferential step and near-step decoration in both cases, although it is less pronounced for Os than Ru. We also investigated the incremental dissolution of the Os from Au(111), to better understand electrochemical dissolution processes in general and to better control the Os deposit structure. The application of controlled electrochemical treatments (cyclic voltammetry up to increasingly positive values) significantly increased the dispersion of the Os deposit by generating smaller, more widely spaced islands. Upon voltammetry up to 0.75 V, the Au(111)/Os surface showed evidence of alloying and the formation of 3-D structures suggestive of strong Os-Os (oxidized) species interactions. The CO stripping results show the Au(111)/Os is not particularly effective for this reaction, but such results help to complete the overall picture of NM-NM catalytic combinations. Although the Au(111)/Os system itself is not catalytically active, the electrochemical manipulation of the deposit structure demonstrated here may be applied to other noble metal/noble metal (NM/NM) catalytic substrates to find optimal deposit morphologies.     

New insights on the Cd UPD on Au(111)

The Cd underpotential deposition (UPD) process on Au(111) was analyzed by means of combined electrochemical measurements and in situ scanning tunneling microscopy (STM). In the underpotential range 300?ΔE (mV) ?400, 2D Cd islands are formed on the fcc regions of the Au(111)‐(√3 × 22) reconstructed surface without lifting the reconstruction. At lower underpotentials, the 2D Cd islands grow and, simultaneously, new 2D islands nucleate and coalesce with the previous ones forming a complete condensed Cd monolayer (ML). STM images and long time polarization experiments performed at ΔE = 70 mV demonstrate the formation of an Au? Cd surface alloy. At ΔE = 10 mV, the formation of the complete Cd ML is accompanied by a significant Au? Cd surface alloying and the kinetic results reveal two different solid‐state diffusion processes. The first one, with a diffusion coefficient D₁ = 4 × 10^?17 cm² s^?1, could be ascribed to the mutual diffusion of Au and Cd atoms through a highly distorted (vacancy‐rich) Au? Cd alloy layer. The second and faster diffusion process (D₂ = 7 × 10^?16 cm² s^?1) is associated with the appearance of an additional peak in the anodic stripping curves and could be attributed to the formation of another Cd_zAu_x alloy phase. Copyright © 2008 John Wiley & Sons, Ltd.     

In situ STM investigation of spinodal decomposition and surface alloying during underpotential deposition of Cd on Au(111) from an ionic liquid

The electrodeposition and anodic dissolution of Cd on Au(111) in an acidic chloroaluminate ionic liquid (MBIC-AlCl(3), 42 : 58 mol%) have been investigated by cyclic voltammetry and in situ STM. In the Cd underpotential deposition region, various nanostructures can be distinguished. At a potential of 0.95 V vs. Al/Al(iii), a transformation from a well ordered AlCl(4)(-) adlayer to a ( radical3 x radical19) superstructure, presumably due to Cd-AlCl(4)(-) coadsorption, is observed. Reducing the potential to 0.45 V, surface alloying of Cd and Au occurs, which is evidenced for the first time by typical spinodal structures occurring both during deposition and dissolution of the surface alloy layer having a hexagonal structure. At still lower potentials below 0.21 V, a layer-by-layer growth of bulk Cd sets in.     

In-situ scanning tunneling microscopy of carbon monoxide adsorbed on Au(111) electrode

In-situ scanning tunneling microscopy (STM) coupled with cyclic voltammetry was used to examine the adsorption of carbon monoxide (CO) molecules on an ordered Au(111) electrode in 0.1 M HClO4. Molecular resolution STM revealed the formation of several commensurate CO adlattices, but the (9 x radical 3) structure eventually prevailed with time. The CO adlayer was completely electrooxidized to CO2 at 0.9 V versus RHE in CO-free 0.1 M HClO(4), as indicated by a broad and irreversible anodic peak which appeared at this potential in a positive potential sweep from 0.05 to 1.6 V. A maximal coverage of 0.3 was estimated for CO admolecules from the amount of charge involved in this feature. Real-time in-situ STM imaging allowed direct visualization of the adsorption process of CO on Au(111) at 0.1 V, showing the lifting of (radical 3 x 22) reconstruction of Au(111) and the formation of ordered CO adlattices. The (9 x radical 3) structure observed in CO-saturated perchloric acid has a coverage of 0.28, which is approximately equal to that determined from coulometry. Switching the potential from 0.1 to -0.1 V restored the reconstructed Au(111) with no change in the (9 x radical 3)-CO adlattice. However, the reconstructed Au(111) featured a pairwise corrugation pattern with two nearest pairs separated by 74 +/- 1 A, corresponding to a 14% increase from the ideal value of 65.6 A known for the ( radical 3 x 22) reconstruction. Molecular resolution STM further revealed that protrusions resulting from CO admolecules in the (9 x radical 3) structure exhibited distinctly different corrugation heights, suggesting that the CO molecules resided at different sites on Au(111). This ordered structure predominated in the potential range between 0.1 and 0.7 V; however, it was converted into new structures of (7 x radical 7) and ( radical 43 x 2 radical 13) on the unreconstructed Au(111) when the potential was held at 0.8 V for ca. 60 min. The coverage of CO adlayer decreased accordingly from 0.28 to 0.13 before it was completely removed from the Au(111) surface at more positive potentials.     

Electrochemical oxidative formation of ordered monolayers of thiol molecules on Au(111) surface

Electrochemical oxidative formation of thiolate monolayers on a Au(111) surface in KOH ethanol solutions of various thiol concentrations is described. The formation process was investigated by electrochemistry, in situ scanning tunneling microscopy (STM), and surface X‐ray diffraction (SXRD). The reductive charge in the linear sweep voltammogram after keeping the potential at +0.1 V increased with holding time and reached the saturated value of 103 µC cm^?2, corresponding to the full monolayer coverage of the ( ) structure. The desorption peak shifted negatively with holding time even after the monolayer was formed, suggesting that ordering of the monolayer requires a much longer time than full coverage adsorption. The herringbone structure, corresponding to the ( × 23) structure, was observed on the Au(111) surface in KOH ethanol solution by in situ STM, which shows that a clean surface was exposed. When hexanethiol ethanol solution was added into the ethanol solution at ?450 mV so that the final thiol concentration was higher than ca. 5 µM, generation of vacancy islands (VIs) was observed, which shows the potentiostatic monolayer formation. When the potential was scanned positively from ?950 mV where a clean reconstructed Au(111) surface was exposed, generation of VIs was observed accompanied by anodic current flow. During both oxidative adsorption and reductive desorption of the monolayer, the shape of the steps of the gold surface changed drastically, which suggests that the gold atoms on the surface are extremely mobile during the monolayer formation. SXRD measurement confirmed the surface reconstruction lifting upon monolayer formation. © 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 199–209; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900002     

Electrochemical self-assembly of melanin films on gold

An electrochemical method for self-assembling melanin films on the Au(111) surface from melanin aggregates in alkaline media is reported. Electrochemical data combined with scanning tunneling microscopy (STM), atomic force microscopy, and Auger electron spectoscopy show that the amount and structure of the deposited melanin film depend on the potential (E) applied to the electrochemical interface and deposition time. Film formation takes place at a noticeable rate at E = -1.0 V (vs SCE). High-resolution STM images at the early stages of growth show small particles, 5-8 nm in size and 0.3-0.4 nm in height, forming ordered arrays that follow closely the Au(111) topography. The size of the melanin particles increases as the film thickness increases, reaching 150 nm for deposits grown for 16 h. The deposited films are electrochemically active, showing well-defined redox couples preceding the hydrogen evolution reaction.     

Spin‐Crossover Complex on Au(111): Structural and Electronic Differences Between Mono‐ and Multilayers

Submono‐, mono‐ and multilayers of the Fe(II) spin‐crossover (SCO) complex [Fe(bpz)₂(phen)] (bpz=dihydrobis(pyrazolyl)borate, phen=1,10‐phenanthroline) have beenprepared by vacuum deposition on Au(111) substrates and investigated with near edge X‐ray absorption fine structure (NEXAFS) spectroscopy and scanning tunneling microscopy (STM). As evidenced by NEXAFS, molecules of the second layer exhibit a thermal spin crossover transition, although with a more gradual characteristics than in the bulk. For mono‐ and submonolayers of [Fe(bpz)₂(phen)] deposited on Au(111) substrates at room temperature both NEXAFS and STM indicate a dissociation of [Fe(bpz)₂(phen)] on Au(111) into four‐coordinate complexes, [Fe(bpz)₂], and phen molecules. Keeping the gold substrate at elevated temperatures ordered monolayers of intact molecules of [Fe(bpz)₂(phen)] are formed which can be spin‐switched by electron‐induced excited spin‐state trapping (ELIESST).     

Partial stripping of Ag atoms from silver bilayer on a Au(111) surface accompanied with the reductive desorption of hexanethiol SAM

The interfacial structures of Ag bilayer prepared by underpotential deposition on Au(111) (Ag(2ML)/Au(111)) were determined by ex situ scanning tunneling microscopy and in situ surface X-ray scattering measurements before and after oxidative adsorption and after reductive desorption of a self-assembled monolayer (SAM) of hexanethiol (C₆SH) in alkaline ethanol solution. While no structural change was observed after oxidative formation of C₆SH SAM on the Ag(2ML)/Au(111) in an ethanol solution containing 20 mM KOH and 0.1 mM C₆SH, some of the Ag atoms in the bilayer were stripped when the SAM was reductively desorbed. Dedicated to Professor J. O’M. Bockris on the occasion of his 85th birthday.     

Comparative investigation of underpotential deposition of Ag from aqueous and ionic electrolytes: An electrochemical and in situ STM study

Underpotential deposition (UPD) of Ag on Au(111) has been studied with two different electrolytes: aqueous 0.1 M H2SO4 solution in comparison with the ionic liquid 1-butyl-3-methylimidazolium chloride BMICl + AlCl3. Of particular interest is the distinct behavior of 2D phase formation at both interfaces, which has been investigated by cyclic and linear sweep voltammetry in combination with in situ electrochemical scanning tunneling microscopy (STM). It is found that one monolayer (ML) of Ag is formed in the UPD region in both electrolytes. In aqueous solution, atomically resolved STM images at 500 mV versus Ag/Ag+ show a (3 x 3) adlayer of Ag, whereas after sweeping the potential just before the commencement of the bulk Ag deposition, a transition from expanded (3 x 3) to pseudomorphic ML of Ag on Au(111) occurs. In BMICl-AlCl3, the first UPD process of Ag exhibits two peaks at 410 and 230 mV indicating that two distinct processes on the surface take place. For the first time, STM images with atomic resolution reveal a transition from an inhomogeneous to an ordered phase with a (square root of 3 x square root of 3)R30 degrees structure and an adsorption of AlCl4- anions having a superlattice of (1.65 x square root of 3)R30 degrees preceding the deposition of Ag.