Ambient pressure photoelectron spectroscopy: a new tool for surface science and nanotechnology

Progress in science often follows or parallels the development of new techniques. The optical microscope helped convert medicine and biology from a speculative activity in old times to today's sophisticated scientific disciplines. The telescope changed the study and interpretation of heavens from mythology to science. X-ray diffraction enabled the flourishing of solid state physics and materials science. The technique object of this review, Ambient Pressure Photoelectron Spectroscopy or APPES for short, has also the potential of producing dramatic changes in the study of liquid and solid surfaces, particularly in areas such as atmospheric, environment and catalysis sciences. APPES adds an important missing element to the host of techniques that give fundamental information, i.e., spectroscopy and microscopy, about surfaces in the presence of gases and vapors, as encountered in industrial catalysis and atmospheric environments. APPES brings electron spectroscopy into the realm of techniques that can be used in practical environments. Decades of surface science in ultra high vacuum (UHV) has shown the power of electron spectroscopy in its various manifestations. Their unique property is the extremely short elastic mean free path of electrons as they travel through condensed matter, of the order of a few atomic distances in the energy range from a few eV to a few thousand eV. As a consequence of this the information obtained by analyzing electrons emitted or scattered from a surface refers to the top first few atomic layers, which is what surface science is all about. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), Ultraviolet photoelectron spectroscopy (UPS), and other such techniques have been used for decades and provided some of the most fundamental knowledge about surface crystallography, composition and electronic structure available today. Unfortunately the high interaction cross section of electrons with matter also prevents them from traveling long distances unscattered in gas environments. Above the millibar pressure range this distance is reduced to less that a millimeter, effectively preventing its use in the most relevant environments, usually between millibars and atmospheric pressures. There is therefore a large gap of several orders of magnitude where information about surfaces is scarce because these powerful electron spectroscopies cannot operate. One characteristic of surfaces in ambient pressure environments is that they are covered by dense layers of molecules, even when their binding energy is weak. Water for example is known to form layers several molecules thick at room temperature in humid environments. Metals readily form oxide films several layers thick in oxygen atmospheres. Dense layers of adsorbed molecules can also be produced in ultra high vacuum, often by the simple and expedient method of cooling the sample to cryogenic temperatures. A large amount of data has been obtained in the past in UHV by surface scientists using this method. While this has provided valuable information it begs the question of whether the structures formed in this manner represent equilibrium structures or metastable ones, kinetically trapped due to high activation energies that cannot be overcome at low temperature. From a thermodynamic point of view is interesting to consider the entropic contribution to the Gibbs free energy, which we can call 'the pressure factor', equal to kT.logP. This factor amounts to a sizeable 0.3 eV difference at room temperature between UHV (<10{sup -8} Pascal) and atmospheric pressures. Such change if free energy can definitely result in changes in surface structure and stability. Entire areas of the phase diagram are out of reach due to the pressure gap. Even when cooling is not necessary, many surface treatments and most chemical reactions necessitate the presence of gases at pressures ranging from millibar to bars. What is the structure and chemical nature of the species formed on the surface in equilibrium with such gases? As we shall illustrate in this review, APPES provides a much needed electron spectroscopy to analyze surface electronic structure and composition in equilibrium with gases

The Nature of the Dissociation Sites of Hydrogen Molecules on Ru(001)

Scanning tunneling microscopy (STM) was used to study the dissociative adsorption of H{sub 2} on Ru(001) near saturation coverage, when the number of residual hydrogen vacancies (i.e., unoccupied Ru sites) is small. We found that H{sub 2} dissociation takes place only on Ru sites where the metal atom is not bound to any H atom. Such active sites are formed when at least 3 H-vacancies aggregate by thermal diffusion. Sites formed by single H-vacancies or pairs of adjoining vacancies were found to be unreactive toward H{sub 2}. As a similar phenomenon was found previously on Pd(111), the present results indicate that the active sites for H2 dissociation share a common characteristic among catalytically active transition metals

A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies

This is the published version. Copyright 2008 American Institute of PhysicsWe present the design and performance of a homebuilt high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope STM for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor 19 cm3 located within an ultrahigh vacuum UHV chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10−13 to several bars and a temperature range of 300–700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm

Imaging and manipulation of nanometer-size liquid droplets by scanning polarization force microscopy

Using atomic force microscopy in noncontact mode, we have imaged nanometer-size liquid droplets of KOH water solutions on the surfaces of highly oriented pyrolitic graphite and mica. On graphite the droplets prefer to be adsorbed on atomic step edges. Droplets on the same step tend to be evenly spaced and of similar size. The droplets can be manipulated by the atomic force microscopy tip allowing the controllable formation of droplet patterns on the surface

When Langmuir is too simple: H-2 dissociation on Pd(111) at high coverage

Recent experiments of H2 adsorption on Pd(111) [T. Mitsui et al., Nature (London) 422, 705 (2003)] have questioned the classical Langmuir picture of second order adsorption kinetics at high surface coverage requiring pairs of empty sites for the dissociative chemisorption. Experiments find that at least three empty sites are needed. Through density functional theory, we find that H2 dissociation is favored on ensembles of sites that involve a Pd atom with no direct interaction with adsorbed hydrogen. Such active sites are formed by aggregation of at least 3 H-free sites revealing the complex structure of the "active sites.

In situ photoelectron spectroscopy study of water adsorption on model biomaterial surfaces

Using in situ photoelectron spectroscopy at near ambient conditions, we compare the interaction of water with four different model biomaterial surfaces: self-assembled thiol monolayers on Au(111) that are functionalized with methyl, hydroxyl, and carboxyl groups, and phosphatidylcholine (POPC) lipid films on Silicon. We show that the interaction of water with biomaterial surfaces is mediated by polar functional groups that interact strongly with water molecules through hydrogen bonding, resulting in adsorption of 0.2-0.3 ML water on the polar thiol films in 700 mTorr water pressure and resulting in characteristic N1s and P2p shifts for the POPC films. Provided that beam damage is carefully controlled, in situ electron spectroscopy can give valuable information about water adsorption which is not accessible under ultra-high vacuum conditions

A new scanning tunneling microscope reactor used for high-pressure and high-temperature catalysis studies

This is the published version. Copyright 2008 American Institute of PhysicsWe present the design and performance of a homebuilt high-pressure and high-temperature reactor equipped with a high-resolution scanning tunneling microscope STM for catalytic studies. In this design, the STM body, sample, and tip are placed in a small high pressure reactor 19 cm3 located within an ultrahigh vacuum UHV chamber. A sealable port on the wall of the reactor separates the high pressure environment in the reactor from the vacuum environment of the STM chamber and permits sample transfer and tip change in UHV. A combination of a sample transfer arm, wobble stick, and sample load-lock system allows fast transfer of samples and tips between the preparation chamber, high pressure reactor, and ambient environment. This STM reactor can work as a batch or flowing reactor at a pressure range of 10−13 to several bars and a temperature range of 300–700 K. Experiments performed on two samples both in vacuum and in high pressure conditions demonstrate the capability of in situ investigations of heterogeneous catalysis and surface chemistry at atomic resolution at a wide pressure range from UHV to a pressure higher than 1 atm