The adsorption behavior of an Cu electroplating additive, 3,3 thiobis-(1-propanesulfonic acid sodium salt) (TBPS) in a process of Cu deposition onto a single crystalline Au(111) surface is studied by an in-situ Surface-Enhanced Infrared Absorption Spectroscopy (SEIRAS). The SEIRAS spectra of the TBPS adlayer on a Cu film is investigated first and compared to that on an Au film. These results are utilized to evaluate the characteristics of TBPS adlayer on the electrode surface during the Cu deposition and stripping processes. The results show that the SEIRAS spectra of TBPS adsorbed on the Cu film resembles closely to that on the Au film, and the most pronounced peaks are symmetric S-O (ss-SO) and asymmetric S-O (as-SO) stretching modes. However, the as-SO band is sharper with a higher intensity on the Cu film. Since the ss-SO and as-SO peaks correspond to the molecular with upright and lie-down orientations, respectively, it implies that the TBPS molecules have higher ratio of lie-down orientation on the Cu film. In the Cu electrodeposition process, the cyclic voltammetry (CV) result shows that the presence of the TBPS in the HClO4 solution can decrease the inhibition effect of HClO4 to the Cu deposition. For the spectra measured at various potential during cathodic and anodic sweeping, an obvious change of the spectra occurs at ca. 0.6 V, the initiation of Cu underpotential deposition (Cu-UPD). For potentials higher and lower than 0.6 V, the spectra are similar, respectively, to those measured for the Au and Cu films. This result indicates that the TBPS molecules originally adsorbing on the Au film transfer to the surface of deposited Cu layer. This inference is also confirmed by the variation in wavenumber and peak intensity of ss-SO and as-SO peaks during the potential sweeping.

The impact of 3,3'-thiobis(1-propanesulfonic acid, sodium salt) (TBPS) on Cu/Au(111) electrodeposition has been investigated by electrochemical methods and scanning tunneling microscopy (STM). Cyclic voltammetry and galvanostatic experiments indicate that Cu growth on Au(111)-which is known to be strongly kinetically hindered in additive-free, aqueous perchloric acid solutions - proceeds significantly faster in the presence of TBPS. The TBPS molecules either ldquofloatrdquo on top of the growing film or become incorporated into the deposit. Complementary in situ STM studies show that Cu underpotential deposition (UPD) proceeds via two distinct mechanisms. One-dimensional growth of Cu stripes was observed between 0.05 and 0.35 V RHE for TBPS-modified Au(111) electrodes. Each stripe is composed of two or three parallel rows of Cu atoms oriented along the main crystallographic directions of the Au(111) substrate. An increase of the TBPS concentration near the solid/liquid interface restricts the Cu stripe growth to a narrow potential regime between 0.3 and 0.35 V RHE and two-dimensional Cu island growth becomes the favored growth mechanism. The latter fully dominates in TBPS-containing electrolyte. Cu growth in the overpotential deposition (OPD) regime results in a smooth Cu film with low surface roughness, in contrast to defect-mediated 3D island growth in additive-free electrolytes.

The impact of 3,3'-thiobis(1-propanesulfonic acid, sodium salt) (TBPS) on Cu/Au(111) electrodeposition has been investigated by electrochemical methods and scanning tunneling microscopy (STM). Cyclic voltammetry and galvanostatic experiments indicate that Cu growth on Au(111) - which is known to be strongly kinetically hindered in additive-free, aqueous perchloric acid solutions - proceeds significantly faster in the presence of TBPS. The TBPS molecules either "float" on top of the growing film or become incorporated into the deposit. Complementary in situ STM studies show that Cu underpotential deposition (UPD) proceeds via two distinct mechanisms. One-dimensional growth of Cu stripes was observed between 0.05 and 0.35 V-RHE for TBPS-modified Au(111) electrodes. Each stripe is composed of two or three parallel rows of Cu atoms oriented along the main crystallographic directions of the Au(111) substrate. An increase of the TBPS concentration near the solid/liquid interface restricts the Cu stripe growth to a narrow potential regime between 0.3 and 0.35 V-RHE and two-dimensional Cu island growth becomes the favored growth mechanism. The latter fully dominates in TBPS-containing electrolyte. Cu growth in the overpotential deposition (OPD) regime results in a smooth Cu film with low surface roughness, in contrast to defect-mediated 3D island growth in additive-free electrolytes. (C) 2011 The Electrochemical Society. [DOI: 10.1149/2.057202jes] All rights reserved.

A novel approach to construct organized structures and tunable electronic properties of poly(3-hexylthiophene) (P3HT) monolayers on Au(111) surfaces was developed based on a self-assembly process in a liquid phase. On a bare Au(111) surface, P3HT adsorbs as a monolayer with a randomly oriented and curvy-wire morphology. When the gold surface was pre-modified by an iodine adlayer (I-Au(111)), the passivation effect of iodine decreases the substrate-adsorbate interaction. As a result, P3HT adsorbs as linear chains, stacking and folding into regular arrays of a polymer bundle. By controlling the electrode at more negative potentials, it is able to desorb the iodine adlayer from the substrate. The remaining P3HT adsorbs onto the Au(111) surface directly, retaining a linear and regular arrangement. However, a different electronic structure is imaged by scanning tunneling microscopy (STM). The scanning tunneling spectroscopy (STS) analysis reveals that this molecular image is associated with a 0.16 eV shift of the Fermi level toward HOMO position, indicating a stronger p-doping characteristic of the adlayer. The phenomenon is ascribed to an iodine-induced p-doping reaction which occurs during the desorption of iodine. This work demonstrates that electrode potential and pre-adsorbed halide adlayers can be effectively used to regulate the arrangement and electronic properties of adsorbed molecules on metallic substrates.

A novel approach to construct organized structures and tunable electronic properties of poly(3-hexylthiophene) (P3HT) monolayers on Au(111) surfaces was developed based on a self-assembly process in a liquid phase. On a bare Au(111) surface, P3HT adsorbs as a monolayer with a randomly oriented and curvy-wire morphology. When the gold surface was pre-modified by an iodine adlayer (I-Au(111)), the passivation effect of iodine decreases the substrate-adsorbate interaction. As a result, P3HT adsorbs as linear chains, stacking and folding into regular arrays of a polymer bundle. By controlling the electrode at more negative potentials, it is able to desorb the iodine adlayer from the substrate. The remaining P3HT adsorbs onto the Au(111) surface directly, retaining a linear and regular arrangement. However, a different electronic structure is imaged by scanning tunneling microscopy (STM). The scanning tunneling spectroscopy (STS) analysis reveals that this molecular image is associated with a 0.16 eV shift of the Fermi level toward HOMO position, indicating a stronger p-doping characteristic of the adlayer. The phenomenon is ascribed to an iodine-induced p-doping reaction which occurs during the desorption of iodine. This work demonstrates that electrode potential and pre-adsorbed halide adlayers can be effectively used to regulate the arrangement and electronic properties of adsorbed molecules on metallic substrates.

The adsorption and self-assembly behaviors of a carboxyl-group-terminated alkanethiol, 11-mercaptoundecanoic acid (MUA), on Au(111) electrodes in an electrochemical system are studied using in situ scanning tunneling microscopy. The effect of applied potential on the phase evolution of the MUA adlayer is investigated and compared with those reported for alkanethiols with various terminal groups. The results show that the MUA molecules initially adsorb in a lie-down orientation, organizing into ordered domains with a stripe structure. With further adsorption of MUA molecules, the alkyl chains lift off from the substrate, forming a more condensed phase with an arrangement of (root 3 x root 3). This phase evolution is similar to those reported for other alkanethiols. However, the adsorption process of MUA is much slower and a disordered transition phase (gamma phase) exists between the stripe and saturation phases. The gamma phase converts back to the stripe phase when the electrode potential is shifted from 0.2 to 0.4 V, following which the phase evolution cannot proceed further to the saturation phase. These results are contrary to those observed for other alkanethiols and are attributed to the interaction of the terminal COOH group with the substrate at positive potentials. Under the electrode potential, the molecules bind to the substrate via both head and end groups, triggering a lie-down orientation and decreasing the mobility of adsorbed molecules. As a result, the adlayer remains in the stripe phase and further phase evolution is inhibited.

The adsorption and self-assembly behaviors of a carboxyl-group-terminated alkanethiol, 11-mercaptoundecanoic acid (MUA), on Au(111) electrodes in an electrochemical system are studied using in situ scanning tunneling microscopy. The effect of applied potential on the phase evolution of the MUA adlayer is investigated and compared with those reported for alkanethiols with various terminal groups. The results show that the MUA molecules initially adsorb in a lie-down orientation, organizing into ordered domains with a stripe structure. With further adsorption of MUA molecules, the alkyl chains lift off from the substrate, forming a more condensed phase with an arrangement of (root 3 x root 3). This phase evolution is similar to those reported for other alkanethiols. However, the adsorption process of MUA is much slower and a disordered transition phase (gamma phase) exists between the stripe and saturation phases. The gamma phase converts back to the stripe phase when the electrode potential is shifted from 0.2 to 0.4 V, following which the phase evolution cannot proceed further to the saturation phase. These results are contrary to those observed for other alkanethiols and are attributed to the interaction of the terminal COOH group with the substrate at positive potentials. Under the electrode potential, the molecules bind to the substrate via both head and end groups, triggering a lie-down orientation and decreasing the mobility of adsorbed molecules. As a result, the adlayer remains in the stripe phase and further phase evolution is inhibited.

Adsorption behaviors of hydroxyl-terminated alkanethiol, 3-mercapto-1-propanol (MPO), and arenethiol, 4-mercaptophenol (MPH), on Au(111) electrodes were studied by cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM). The effects of the molecular structure and the chain length on the characteristics of the self-assembled monolayers (SAMs) were investigated by comparison with the results of 11-mercapto-1-undecanol (MUO) and 6-mercapto-1-hexanol (MHO) reported in the literature. All the alkanethiol SAMs have the same coverage ratio (0.33 ML). For MUO which has a longer chain length, a hexagonal lattice, the (root 3 x root 3) structure was observed. However, for shorter thiols (MHO and MPO), the adsorbed molecules exhibit different contrasts under the imaging of STM, ascribed to the different conformations of adsorbed molecules. The CV results indicated that a longer chain length triggers a SAM with higher adhesion and higher resistance to the charge transfer across a SAM. For the SAM of arenethiol, MPH, the pi-pi stacking interaction of the phenyl ring leads to a lower surface mobility of thiol/Au complexes, lower coverage ratio, and less uniform structure of the adlayer. Furthermore, the vacancy islands commonly observed on alkanethiol-modified Au(111) electrodes do not appear on the MPH-modified surface. Instead, 2-dimensional patch islands formed on the terrace due to the aggregation of moveable MPH/Au complexes.

Ultra-thin platinum films were deposited on indium tin oxide (ITO) substrates in a sputtering process and used as counter electrodes of dye-sensitized solar cells. The nano-structured Pt film not only has a high transmittance (75%), but also has a lower charge-transfer resistance compared with that of thick Pt films. Under front-side illumination, the synergistic effects of the nano-structured Pt film (1.4 nm) and a reflective aluminum foil can increase the efficiency of a normal cell from 6.8 to 7.9%. For the back-side illumination, the efficiency achieved by using the present strategy is 6.6%, which is comparable to the front-side illuminated efficiency of DSSCs using thick Pt films (ca. 6.8%). (C) 2010 Elsevier B.V. All tights reserved.

In situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV) were used to study the adsorption of 3-mercapto-1-propanesulfonic acid (MPS) and bis(3-sulfopropyl)-disulfide (SPS) on Au(111) electrode in a HClO(4) aqueous solution. Chloride ions were introduced into the electrolyte solution, and their effect on the adsorption behavior of MPS and SPS was investigated. The CV results show that SPS and MPS molecules preferentially adsorb on the Au(111) surface compared to chloride ions, and furthermore, chloride ion can induce the adsorption of thiol molecules on the Au(111) surface. In the absence of chloride, no adsorption phase of SPS (or MPS) adlayer can be imaged by STM at low potentials. Raising electrode potential leads to the appearance of disordered adsorption phase at ca. 0.4 V (vs RH E) and ordered adlattices at ca. 0.8 V. In the presence of chloride, ordered adsorption structures of SPS and MPS appear at a lower potential (0.2 V), implying the enhancement effect of chloride to the thiol adsorption. It is inferred that the presence of chloride ions triggers a more positively charged gold surface, enhancing the reaction rate of thiol adsorption. Furthermore, the presence of chloride also leads to a decrease in the thiol electrolyte interaction, due to the high solvation effect of chloride ions, which promotes the adsorption of SPS and MPS onto the Au surface. With further elevation of electrode potential, electrostatic interaction leads to coadsorption of chloride ions into the adlayer, as well as orientation changes of the ad-molecules. As a result, the ordered adlattice was disrupted and disappeared at ca. 0.5 V.

The study purpose was to examine the validities and reliabilities of the Chinese-versions Frommelt Attitudes Toward Care of the Dying Scale (Attitudes Scale) and Caregiving Behaviors Scale for End-of-Life Patients and Families (Behaviors Scale). The scales were tested in a convenience sample of 318 nurses with >= 6 months work experience at three hospitals. Cronbach's alphas of the Attitudes and Behaviors Scales were .90 and .96, respectively. Each scale had Kaiser-Meyer-Olkin index >.85 and Bartlett's test of sphericity >4000 (p < .001). Attitudes Scale loaded on three factors: respecting and caring for dying patients and families, avoiding care of the dying, and involving patients and families in end-of-life care. The Behaviors Scale loaded on two factors: supporting dying patients and families, and helping families cope with grief. Factor loadings for both scales were >= 49. Both Attitudes and Behaviors Scales are reliable and valid for evaluating nurses' attitudes and caregiving behaviors for the dying.

Self-assembled monolayers (SAMs) of 6-mercapto-1-hexanol (MHO) on an Au(111) electrode were prepared in an electrochemical system. The adsorption behavior of MHO and the time-dependent organization of the SAM were investigated by in situ scanning tunneling microscopy (STM) and cyclic voltammetry (CV). The results show that a potential higher than 0.28 V (relative to RHE) is required to induce the adsorption of MHO. At 0.28 V, the MHO molecules adsorb in a flat-lying orientation, forming an ordered striped phase with a molecular arrangement of (8 x v 3). However, the adlayer is not stable at this potential. The adsorbed striped phase may recover to the herringbone feature of the gold substrate due to the desorption of adsorbed MHO. At a higher potential (0.35 V), the adlayer becomes stable and can undergo a phase evolution from the striped phase to a condensed structure, identified as c(3 x 2 root 3). This structure can also be described as a c(4 x 2) superlattice of a (root 3 x root 3) R30 degrees hexagonal adlattice. The surface coverage of the MHO SAM is identical to the saturated structure of an 11-mercapto-1-undecanol (MUO) SAM reported in a previous work, (root 3 x root 3) R30 degrees. However, the STM image of MHO adlayer shows a modulation in intensity, reflecting the presence of various conformations of adsorbed molecules. This result is attributed to the shorter chain length of MHO, which gives a weaker van der Waals interaction between adsorbed molecules. This effect also results in a higher charge permeability across the adlayer and a lower striping potential to an MHO SAM.

Self-assembled monolayers (SAMs) of 3,3'-thiobis(1-propane-sulfonic acid, sodium salt) (TBPS) on Au(111) electrodes have been characterized by scanning tunneling microscopy and cyclic voltammetry in aqueous perchloric acid solutions. TBPS exhibits an adsorption behavior typically observed for dialkyl sulfides including intact adsorption and low coverage phases with molecules predominantly lying flat on the surface. On the other hand, an untypical chemical bond and well domains were determined which resemble the characteristics of alkenethiol SAMs. When the adlayer was prepared at its open circuit potential (OCP), a (6 x 3 root 3) TBPS adlayer phase was observed at potentials E > 0.7 V(RHE) in TBPS-free electrolyte. At more cathodic potentials, the adlayer transforms irreversible to a disordered phase. In contrast, in situ STM studies in TBPS-containing electrolyte reveal a very complex, potential-dependent adsorption behavior. With increasing electrode potential, the structure of the adlayer transforms in sequence from a disordered phase sigma, to a low coverage stripe phase alpha, to a high coverage stripe phase beta, and finally to a disordered aggregate phase sigma(a). The re verse cathodic sweep shows transitions from sigma(a) to beta, back to sigma(a), and to an ordered adlayer phase gamma. All of these phases significantly differ from the (6 x 3 root 3) phase oil are not transient phases at OCP. This behavior is attributed to the influence of the electrode potential on intermolecular and molecule - substrate interaction, as well is on the TBPS coverage Furthermore, the cathodic deposition of Au-TBPS complexes results in the formation of Au islands with fractal morphology.