Surface Passivation by Quantum Exclusion: On the Quantum Efficiency and Stability of Delta-Doped CCDs and CMOS Image Sensors in Space.

Radiation-induced damage and instabilities in back-illuminated silicon detectors have proved to be challenging in multiple NASA and commercial applications. In this paper, we develop a model of detector quantum efficiency (QE) as a function of Si-SiO2 interface and oxide trap densities to analyze the performance of silicon detectors and explore the requirements for stable, radiation-hardened surface passivation. By analyzing QE data acquired before, during, and after, exposure to damaging UV radiation, we explore the physical and chemical mechanisms underlying UV-induced surface damage, variable surface charge, QE, and stability in ion-implanted and delta-doped detectors. Delta-doped CCD and CMOS image sensors are shown to be uniquely hardened against surface damage caused by ionizing radiation, enabling the stability and photometric accuracy required by NASA for exoplanet science and time domain astronomy.

Characterization of the Percival detector with soft X-rays.

In this paper the back-side-illuminated Percival 2-Megapixel (P2M) detector is presented, along with its characterization by means of optical and X-ray photons. For the first time, the response of the system to soft X-rays (250 eV to 1 keV) is presented. The main performance parameters of the first detector are measured, assessing the capabilities in terms of noise, dynamic range and single-photon discrimination capability. Present limitations and coming improvements are discussed.

Single Photon Counting UV Solar-Blind Detectors Using Silicon and III-Nitride Materials.

Ultraviolet (UV) studies in astronomy, cosmology, planetary studies, biological and medical applications often require precision detection of faint objects and in many cases require photon-counting detection. We present an overview of two approaches for achieving photon counting in the UV. The first approach involves UV enhancement of photon-counting silicon detectors, including electron multiplying charge-coupled devices and avalanche photodiodes. The approach used here employs molecular beam epitaxy for delta doping and superlattice doping for surface passivation and high UV quantum efficiency. Additional UV enhancements include antireflection (AR) and solar-blind UV bandpass coatings prepared by atomic layer deposition. Quantum efficiency (QE) measurements show QE > 50% in the 100-300 nm range for detectors with simple AR coatings, and QE ≅ 80% at ~206 nm has been shown when more complex AR coatings are used. The second approach is based on avalanche photodiodes in III-nitride materials with high QE and intrinsic solar blindness.

Impact of branching on the supramolecular assembly of thioethers on Au(111).

Alkanethiolate monolayers are one of the most comprehensively studied self-assembled systems due to their ease of preparation, their ability to be functionalized, and the opportunity to control their thickness perpendicular to the surface. However, these systems suffer from degradation due to oxidation and defects caused by surface etching and adsorbate rotational boundaries. Thioethers offer a potential alternative to thiols that overcome some of these issues and allow dimensional control of self-assembly parallel to the surface. Thioethers have found uses in surface modification of nanoparticles, and chiral thioethers tethered to catalytically active surfaces have been shown to enable enantioselective hydrogenation. However, the effect of structural, chemical, and chiral modifications of the alkyl chains of thioethers on their self-assembly has remained largely unstudied. To elucidate how molecular structure, particularly alkyl branching and chirality, affects molecular self-assembly, we compare four related thioethers, including two pairs of structural isomers. The self-assembly of structural isomers N-butyl methyl sulfide and tert-butyl methyl sulfide was studied with high resolution scanning tunneling microscopy (STM); our results indicate that both molecules form highly ordered arrays despite the bulky tert-butyl group. We also investigated the effect of intrinsic chirality in the alkyl tails on the adsorption and self-assembly of butyl sec-butyl sulfide (BSBS) with STM and density functional theory and contrast our results to its structural isomer, dibutyl sulfide. Calculations provide the relative stability of the four stereoisomers of BSBS and STM imaging reveals two prominent monomer forms. Interestingly, the racemic mixture of BSBS is the only thioether we have examined to date that does not form highly ordered arrays; we postulate that this is due to weak enantiospecific intermolecular interactions that lead to the formation of energetically similar but structurally different assemblies. Furthermore, we studied all of the molecules in their monomeric molecular rotor form, and the surface-adsorbed chirality of the three asymmetric thioethers is distinguishable in STM images.

Metal-dielectric filters for solar-blind silicon ultraviolet detectors.

We report on the fabrication of metal-dielectric thin film stacks deposited directly onto silicon substrates for use as ultraviolet bandpass filters. Integration of these filters onto silicon improves the admittance matching of the structure when compared to similar designs fabricated on transparent substrates, leading to higher peak transmission or improved out-of-band rejection if used with a Si-based sensor platform. Test structures fabricated with metallic Al and atomic layer deposited Al2O3 were characterized with spectroscopic ellipsometry and agree well with optical models. These models predict transmission as high as 90% the spectral range of 200-300 nm for simple three-layer coatings.

Controlling a spillover pathway with the molecular cork effect.

Spillover of reactants from one active site to another is important in heterogeneous catalysis and has recently been shown to enhance hydrogen storage in a variety of materials. The spillover of hydrogen is notoriously hard to detect or control. We report herein that the hydrogen spillover pathway on a Pd/Cu alloy can be controlled by reversible adsorption of a spectator molecule. Pd atoms in the Cu surface serve as hydrogen dissociation sites from which H atoms can spillover onto surrounding Cu regions. Selective adsorption of CO at these atomic Pd sites is shown to either prevent the uptake of hydrogen on, or inhibit its desorption from, the surface. In this way, the hydrogen coverage on the whole surface can be controlled by molecular adsorption at a minority site, which we term a 'molecular cork' effect. We show that the molecular cork effect is present during a surface catalysed hydrogenation reaction and illustrate how it can be used as a method for controlling uptake and release of hydrogen in a model storage system.

Effect of head-group chemistry on surface-mediated molecular self-assembly.

Surface molecular self-assembly is a fast advancing field with broad applications in sensing, patterning, device assembly, and biochemical applications. A vast number of practical systems utilize alkane thiols supported on gold surfaces. Whereas a strong Au-S bond facilitates robust self-assembly, the interaction is so strong that the surface is reconstructed, leaving etch pits that render the monolayers susceptible to degradation. By using different head group elements to adcust the molecule-surface interaction, a vast array of new systems with novel properties may be formed. In this paper we use a carefully chosen set of molecules to make a direct comparison of the self-assembly of thioether, selenoether, and phosphine species on Au(111). Using the herringbone reconstruction of gold as a sensitive readout of molecule-surface interaction strength, we correlate head-group chemistry with monolayer (ML) properties. It is demonstrated that the hard/soft rules of inorganic chemistry can be used to rationalize the observed trend of molecular interaction strengths with the soft gold surface, that is, P>Se>S. We find that the structure of the monolayers can be explained by the geometry of the molecules in terms of dipolar, quadrupolar, or van der Waals interactions between neighboring species driving the assembly of distinct ordered arrays. As this study directly compares one element with another in simple systems, it may serve as a guide for the design of self-assembled monolayers with novel structures and properties.

Rediscovering cobalt's surface chemistry.

Cobalt is an active metal for a variety of commercially and environmentally significant heterogeneously catalysed processes. Despite its importance, Co's surface chemistry is less studied compared to other key industrial catalyst metals. This stems in part from the difficulties associated with single crystal preparation and stability. Recent advances in scanning probe microscopy have enabled the atomic scale study of the structural, electronic, and magnetic properties of well-defined Co nanoparticles on metal substrates. Such systems offer an excellent platform to investigate the adsorption, diffusion, dissociation, and reaction of catalytically relevant molecules. Here we discuss the current understanding of metal-supported Co nanoparticles, review the limited literature on molecular adsorption, and suggest ways that they can be used to explore Co's rich surface chemistry. Our discussion is accompanied by new high resolution scanning tunnelling microscopy data from our group, which illustrate some of the interesting properties of these complex systems.

Viewing and inducing symmetry breaking at the single-molecule limit.

Symmetry breaking by photons, electrons, and molecular interactions lies at the heart of many important problems as varied as the origin of homochiral life to enantioselective drug production. Herein we report a system in which symmetry breaking can be induced and measured in situ at the single-molecule level using scanning tunneling microscopy. We demonstrate that electrical excitation of a prochiral molecule on an achiral surface produces large enantiomeric excesses in the chiral adsorbed state of up to 39%. The degree of symmetry breaking was monitored as a function of scanning probe tip state, and the results revealed that enantiomeric excesses are correlated with the intrinsic chirality in scanning probe tips themselves, as evidenced by height differences between single molecule enantiomers. While this work has consequences for the study of two-dimensional chirality, more importantly, it offers a new method for interrogating the coupling of photons, electrons, and combinations of physical fields to achiral starting systems in a reproducible manner. This will allow the mechanism of chirality transfer to be studied in a system in which enantiomeric excesses are quantified accurately by counting individual molecules.

Spontaneous transmission of chirality through multiple length scales.

The hierarchical transfer of chirality in nature, from the nano-, to meso-, to macroscopic length scales, is very complex, and as of yet, not well understood. The advent of scanning probes has allowed chirality to be monitored at the single molecule or monolayer level and has opened up the possibility to track enantiospecific interactions and chiral self-assembly with molecular-scale detail. This paper describes the self-assembly of a simple, model molecule (naphtho[2,3-a]pyrene) that is achiral in the gas phase, but becomes chiral when adsorbed on a surface. This polyaromatic hydrocarbon forms a stable and reversibly ordered system on Cu(111) in which the transmission of chirality from single surface-bound molecules to complex 2D chiral architectures can be monitored as a function of molecular packing density and surface temperature. In addition to the point chirality of the surface-bound molecule, the unit cell of the molecular domains was also found to be chiral due to the incommensurate alignment of the molecular rows with respect to the underlying metal lattice. These molecular domains always aggregated in groups of three, all of the same chirality, but with different rotational orientations, forming homochiral "tri-lobe" ensembles. At a larger length scale, these tri-lobe ensembles associated with nearest-neighbor tri-lobe units of opposite chirality at lower packing densities before forming an extended array of homochiral tri-lobe ensembles at higher converges. This system displayed chirality at a variety of size scales from the molecular (≈1 nm) and domain (≈5 nm) to the tri-lobe ensemble (≈10 nm) and extended array (>25 nm) levels. The chirality of the tri-lobe ensembles dictated how the overall surface packing occurred and both homo- and heterochiral arrays could be reproducibly and reversibly formed and interchanged as a function of surface coverage. Finally, these chirally templated surfaces displayed remarkable enantiospecificity for naphtho[2,3-a]pyrene molecules adsorbed in the second layer. Given its simplicity, reversibility, and rich degree of order, this system represents an ideal test bed for the investigation of symmetry breaking and the hierarchical transmission of chirality through multiple length scales.

Aluminum Precursor Interactions with Alkali Compounds in Thermal Atomic Layer Etching and Deposition Processes.

Surface fluorination and volatilization using hydrogen fluoride and trimethyaluminum (TMA) is a useful approach to the thermal atomic layer etching of Al2O3. We have previously shown that significant enhancement of the TMA etching effect occurs when performed in the presence of lithium fluoride chamber-conditioning films. Now, we extend this enhanced approach to other alkali halide compounds including NaCl, KBr, and CsI. These materials are shown to have varying capacities for the efficient removal of AlF3 and ultimately lead to larger effective Al2O3 etch rates at a given substrate temperature. The most effective compounds allow for continuous etching of Al2O3 at substrate temperatures lower than 150 °C, which can be a valuable route for processing temperature-sensitive substrates and for improving the selectivity of the etch over other materials. The strong interaction between TMA and alkali halide materials also results in material-selective thin-film deposition at these reduced substrate temperatures. We discuss possible mechanisms of this etching enhancement and prospects for extending this approach to other material systems. The consequences of using TMA as an ALD and ALE precursor are discussed in the context of interface engineering for alkali-containing substrates such as lithium battery materials.

Dynamics of molecular adsorption and rotation on nonequilibrium sites.

It is generally accepted that important events on surfaces such as diffusion and reactions can be adsorption site dependent. However, due to their short lifetime and low concentration in most systems, adsorbates on nonequilibrium adsorption sites remain largely understudied. Using low-temperature scanning tunneling microscopy, site-dependent adsorption is shown for the molecule butyl methyl sulfide, which is trapped in multiple metastable adsorption sites upon deposition onto a Au(111) surface at 5 K. As this molecule does not have enough energy to diffuse to its preferred adsorption site on the surface, it is possible to study the behavior of individual molecules in a variety of nonequilibrium sites. Here we present atomic-scale data of the same chemical species in three independent, metastable adsorption sites and equilibration to a single equilibrium site as a function of either electrical or thermal excitation. Butyl methyl sulfide exhibits distinctly different physical properties at all four adsorption sites, including rotational dynamics and appearance in scanning tunneling microscopy (STM) images. An energy profile is proposed for the adsorption and equilibration of these species, and a correlation is drawn between rotational barrier and adsorption energy.

Visualization of compression and spillover in a coadsorbed system: syngas on cobalt nanoparticles.

Competitive adsorption and lateral pressure between surface-bound intermediates are important effects that dictate chemical reactivity. Lateral, or two-dimensional, pressure is known to promote reactivity by lowering energetic barriers and increasing conversion to products. We examined the coadsorption of CO and H2, the two reactants in the industrially important Fischer-Tropsch synthesis, on Co nanoparticles to investigate the effect of two-dimensional pressure. Using scanning tunneling microscopy, we directly visualized the coadsorption of H and CO on Co, and we found that the two adsorbates remain in segregated phases. CO adsorbs on the Co nanoparticles via spillover from the Cu(111) support, and when deposited onto preadsorbed adlayers of H, CO exerts two-dimensional pressure on H, compressing it into a higher-density, energetically less-preferred structure. By depositing excess CO, we found that H on the Co surface is forced to spill over onto the Cu(111) support. Thus, spillover of H from Co onto Cu, where it would not normally reside due to the high activation barrier, is preferred over desorption. We corroborated the mechanism of this spillover-induced displacement by calculating the relevant energetics using density functional theory, which show that the displacement of H from Co is compensated for by the formation of strong CO-Co bonds. These results may have significant ramifications for Fischer-Tropsch synthesis kinetics on Co, as the segregation of CO and H, as well as the displacement of H by CO, limits the interface between the two molecules.

Molecular-scale perspective of water-catalyzed methanol dehydrogenation to formaldehyde.

Methanol steam reforming is a promising reaction for on-demand hydrogen production. Copper catalysts have excellent activity and selectivity for methanol conversion to hydrogen and carbon dioxide. This product balance is dictated by the formation and weak binding of formaldehyde, the key reaction intermediate. It is widely accepted that oxygen adatoms or oxidized copper are required to activate methanol. However, we show herein by studying a well-defined metallic copper surface that water alone is capable of catalyzing the conversion of methanol to formaldehyde. Our results indicate that six or more water molecules act in concert to deprotonate methanol to methoxy. Isolated palladium atoms in the copper surface further promote this reaction. This work reveals an unexpected role of water, which is typically considered a bystander in this key chemical transformation.

Molecular-scale surface chemistry of a common metal nanoparticle capping agent: triphenylphosphine on Au(111).

Phosphine-stabilized Au clusters have been extensively studied and are used in various applications due to their unique structural, catalytic, and electronic properties. Triphenylphosphine (PPh(3)) is a key stabilizing ligand in the synthesis of Au nanoclusters. Despite its intense use in nanoparticle synthesis protocols, little is known regarding its surface chemistry, monolayer structure, density, and packing arrangement, all of which are important descriptors of functionality. Here, in contrast to sparse earlier investigations, we report that PPh(3) forms very ordered structures on Au(111). Atomic-scale imaging reveals that monolayer formation is accompanied by a partial lifting of the Au(111) surface reconstruction and ejection of extra Au atoms in the surface layer. Interestingly, these atoms are trapped and stabilized as two-dimensional Au nanoislands within the molecular layer. This behavior is in contrast to thiols, also common capping agents, which tend to remove Au atoms beyond those extra atoms present in the native reconstruction and form vacancy islands on the surface. Our data illustrate PPh(3)'s milder reactivity and reveal a new picture of its packing structure. These results shed new light on the surface chemistry of this important ligand for organic, organometallic, and nanoparticle synthesis.

Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations.

Facile dissociation of reactants and weak binding of intermediates are key requirements for efficient and selective catalysis. However, these two variables are intimately linked in a way that does not generally allow the optimization of both properties simultaneously. By using desorption measurements in combination with high-resolution scanning tunneling microscopy, we show that individual, isolated Pd atoms in a Cu surface substantially lower the energy barrier to both hydrogen uptake on and subsequent desorption from the Cu metal surface. This facile hydrogen dissociation at Pd atom sites and weak binding to Cu allow for very selective hydrogenation of styrene and acetylene as compared with pure Cu or Pd metal alone.

Quantum tunneling enabled self-assembly of hydrogen atoms on Cu(111).

Atomic and molecular self-assembly are key phenomena that underpin many important technologies. Typically, thermally enabled diffusion allows a system to sample many areas of configurational space, and ordered assemblies evolve that optimize interactions between species. Herein we describe a system in which the diffusion is quantum tunneling in nature and report the self-assembly of H atoms on a Cu(111) surface into complex arrays based on local clustering followed by larger scale islanding of these clusters. By scanning tunneling microscope tip-induced scrambling of H atom assemblies, we are able to watch the atomic scale details of H atom self-assembly in real time. The ordered arrangements we observe are complex and very different from those formed by H on other metals that occur in much simpler geometries. We contrast the diffusion and assembly of H with D, which has a much slower tunneling rate and is not able to form the large islands observed with H over equivalent time scales. Using density functional theory, we examine the interaction of H atoms on Cu(111) by calculating the differential binding energy as a function of H coverage. At the temperature of the experiments (5 K), H(D) diffusion by quantum tunneling dominates. The quantum-tunneling-enabled H and D diffusion is studied using a semiclassically corrected transition state theory coupled with density functional theory. This system constitutes the first example of quantum-tunneling-enabled self-assembly, while simultaneously demonstrating the complex ordering of H on Cu(111), a catalytically relevant surface.

Experimental demonstration of a single-molecule electric motor.

For molecules to be used as components in molecular machines, methods that couple individual molecules to external energy sources and that selectively excite motion in a given direction are required. Significant progress has been made in the construction of molecular motors powered by light and by chemical reactions, but electrically driven motors have not yet been built, despite several theoretical proposals for such motors. Here we report that a butyl methyl sulphide molecule adsorbed on a copper surface can be operated as a single-molecule electric motor. Electrons from a scanning tunnelling microscope are used to drive the directional motion of the molecule in a two-terminal setup. Moreover, the temperature and electron flux can be adjusted to allow each rotational event to be monitored at the molecular scale in real time. The direction and rate of the rotation are related to the chiralities of both the molecule and the tip of the microscope (which serves as the electrode), illustrating the importance of the symmetry of the metal contacts in atomic-scale electrical devices.

Time-resolved studies of individual molecular rotors.

Thioether molecular rotors show great promise as nanoscale models for exploring the fundamental limits of thermally and electrically driven molecular rotation. By using time-resolved measurements which increase the time resolution of the scanning tunneling microscope we were able to record the dynamics of individual thioether molecular rotors as a function of surface structure, rotor chemistry, thermal energy and electrical excitation. Our results demonstrate that the local surface structure can have a dramatic influence on the energy landscape that the molecular rotors experience. In terms of rotor structure, altering the length of the rotor's alkyl tails allowed the origin of the barrier to rotation to be more fully understood. Finally, time-resolved measurement of electrically excited rotation revealed that vibrational excitation of a C-H bond in the rotor's alkyl tail is an efficient channel with which to excite rotation, and that the excitation is a one-electron process.