Cluster Beam Research Articles

A Review on Preparation of Palladium Oxide Films

Fabrication aspects of PdO thin films and coatings are reviewed here. The work provides and organizes the up-to-date information on the methods to obtain the films. In recent years, the interest in Pd oxide for different applications has increased. Since Pd can be converted into PdO, it is instructive to pay attention to the preparation of the pure and the alloyed Pd films, heterostructures, and nanoparticles synthesized on different substrates. The development of PdO films is presented from the early reports on coatings’ formation by oxidation of Pd foils and wires to present technologies. Modern synthesis/growth routes are gathered into chemical and physical categories. Chemical methods include hydrothermal, electrochemical, electroless deposition, and coating methods, such as impregnation, precipitation, screen printing, ink jet printing, spin or dip coating, chemical vapor deposition (CVD), and atomic layer deposition (ALD), while the physical ones include sputtering and cathodic arc deposition, laser ablation, ion or electron beam-induced deposition, evaporation, and supersonic cluster beam deposition. Analysis of publications indicates that many as-deposited Pd or Pd-oxide films are granular, with a high variety of morphologies and properties targeting very different applications, and they are grown on different substrates. We note that a comparative assessment of the challenges and quality among different films for a specific application is generally missing and, in some cases, it is difficult to make a distinction between a film and a randomly oriented, powder-like (granular), thin compact material. Textured or epitaxial films of Pd or PdO are rare and, if orientation is observed, in most cases, it is obtained accidentally. Some practical details and challenges of Pd oxidation toward PdO and some specific issues concerning application of films are also presented.

Reactive Gas Cluster Ion Beams for Enhanced Drug Analysis by Secondary Ion Mass Spectrometry.

In this study, we investigate the formation and composition of Gas Cluster Ion Beams (GCIBs) and their application in Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis. We focus on altering the carrier gas composition, leading to the formation of (Ar/CO2)n or (H2O)n GCIBs. Our results demonstrate that the addition of a reactive species (CO2) to water GCIBs significantly enhances the secondary ion yield of small pharmaceutical compounds in the positive ion mode. In negative ion mode, the addition of CO2 resulted in either a positive enhancement or no effect, depending on the sample. However, an excess of CO2 in the carrier gas leads to the formation of carbon dioxide clusters, resulting in reduced yields compared to that of water cluster beams. Cluster size also plays a crucial role in overall yields. In a simple two-drug system, CO2-doped water clusters prove effective in mitigating matrix effects in positive ion mode compared to pure water cluster, while in negative ion mode, this effect is limited. These clusters are also applied to the analysis of drugs in a biological matrix, leading to more quantitative measurements as shown by a better fitting calibration curve. Overall, the doping of water clusters with small amounts of a reactive gas demonstrates promising benefits for higher sensitivity, higher resolution molecular analysis, and imaging using ToF-SIMS. The effectiveness of these reactive cluster beams varies depending on the experimental parameters and sample type.

Highly Selective Dual-Atom Pd Heterogeneous Catalyst Prepared by Size-Selected Cluster Beam

Highly Selective Dual-Atom Pd Heterogeneous Catalyst Prepared by Size-Selected Cluster Beam

The effect of surface states accumulation on photo-electrochemical performances of Bi24Fe2O39 grown by supersonic beams

Holes accumulation on the surface of bismuth ferrite oxides (BFO) photoanodes for photoelectrochemical (PEC) water splitting (WS) is one of the major issues limiting the overall cell efficiency. However, among the various BFO crystal structures, no evidence of this mechanism has been reported for Bi24Fe2O39, a scarcely investigated phase. Herein we characterize the morphological, structural and PEC properties of 100 nm thick nanogranular films of a Bi24Fe2O39 single phase synthesized by supersonic cluster beam deposition. The films were tested as photoanodes for the WS reaction in KOH and Na2SO4 + Na2SO3 electrolytes. The PEC data provide direct evidence of holes accumulation on the surface of the material with increasing applied biases. The interesting performances of this material at low biases suggest a possible use as photocatalyst under visible light irradiation.

Oxidation behavior and atomic structural transition of size-selected coalescence-resistant tantalum nanoclusters

Herein a series of size-selected Ta N (N = 147, 309, 561, 923, 1415, 2057, 6525, 10 000, 20 000) clusters are generated using a gas-phase condensation cluster beam source equipped with a lateral time-of-flight mass-selector. Aberration-corrected scanning transmission electron microscopy (AC-STEM) imaging reveals good thermal stability of Ta N clusters in this study. The oxidation-induced amorphization is observed from AC-STEM imaging and further demonstrated through x-ray photoelectron spectroscopy and energy-dispersive spectroscopy. The oxidized Ta predominantly exists in the +5 oxidation state and the maximum spontaneous oxidation depth of the Ta cluster is observed to be 5 nm under prolonged atmosphere exposure. Furthermore, the size-dependent sintering and crystallization processes of oxidized Ta N clusters are observed with an in situ heating technique, and eventually, ordered structures are restored. As the temperature reaches 1300 °C, a fraction of oxidized Ta309 clusters exhibit decahedral and icosahedral structures. However, the five-fold symmetry structures are absent in larger clusters, instead, these clusters exhibit ordered structures resembling those of the crystalline Ta2O5 films. Notably, the sintering and crystallization process occurs at temperatures significantly lower than the melting point of Ta and Ta2O5, and the ordered structures resulting from annealing remain well-preserved after six months of exposure to ambient conditions.

The role of coalescence and ballistic growth on in-situ electrical conduction of cluster-assembled nanostructured Sn films

The electrical conduction of nanostructured Sn films assembled via Supersonic Cluster Beam Deposition is studied in-situ during film growth. The kinetic energy of Sn nanoparticles, in combination with low melting point of Sn, promotes coalescence phenomena, enabling the investigation of their impact on film morphology and on percolation threshold. A percolation threshold occurring at thicknesses much larger than the dimensions of Sn nanoparticles suggests that coalescence leads to the growth of disconnected, island-like structures. The deposition rate is found to influence coalescence dynamics during the early stages of film growth, allowing for the tuning of film microstructure from a more compact, island-like morphology to a more porous structure. The percolation threshold shifts accordingly from 24 nm to 3 nm film thickness. Upon completion of the percolation phase, film resistivity settles at values 2–3 orders of magnitude larger than that of bulk Sn, attributed to the nanogranular nature of cluster-assembled films. During the “3D conduction” phase, resistivity exhibits an increasing trend with thickness following a power law with an exponent value of 0.76–0.78. This behavior is attributed to the decrease in the density of interconnections between particles in the topmost layer during film growth, consistent with expectations in ballistic growth processes.

Innovative Thermocatalytic H2 Sensor with Double-Sided Pd Nanocluster Films on an Ultrathin Mica Substrate.

Hydrogen (H2) is crucial in the future global energy landscape due to its eco-friendly properties, but its flammability requires precise monitoring. This study introduces an innovative thermocatalytic H2 sensor utilizing ultrathin mica sheets as substrates, coated on both sides with Pd nanocluster (NC) films. The ultrathin mica substrate ensures robustness and flexibility, enabling the sensor to withstand high temperatures and mechanical deformation. Additionally, it simplifies the fabrication process by eliminating the need for complex microelectro-mechanical systems (MEMS) technology. Constructed through cluster beam deposition, the sensor exhibits exceptional characteristics, including a wide concentration range (from 500 ppm to 4%), rapid response and recovery times (3.1 and 2.4 s for 1% H2), good selectivity, high stability, and repeatability. The operating temperature can be as low as 40 °C, achieving remarkably low power consumption. The study explores the impact of double-sided versus single-sided catalytic layers, revealing significantly higher sensitivity and response with the double-sided configuration due to the increased catalytic surface area. Additionally, the research investigates the relationship between the deposition amount of Pd NCs and the sensor's sensitivity, identifying an optimal value that maximizes performance without excessive use of Pd. The sensor's innovative design and excellent performance position it as a promising candidate for meeting the demands of a hydrogen-based energy economy.

Intermediate tin oxide in stable core-shell structures by room temperature oxidation of cluster-assembled nanostructured Sn films

Room temperature oxidation of cluster-assembled nanostructured Sn films obtained by supersonic cluster beam deposition was investigated. Sn clusters smaller than about 10 nm are observed to be fully oxidized while in larger ones, as well as in Sn islands formed by clusters coalescence, completion of Cabrera-Mott process is prevented resulting in partial oxidation. Core-shell structures are therefore obtained, with shell thickness of about 4 nm. Core is composed by highly ordered, tetragonal β-tin, with micro-strain of 0.16 %, while shell is composed of tin oxides, where similar quantity of both Sn oxidation states Sn2+ and Sn4+ are observed, according to XPS. The presence in the samples of metallic tin, SnO, and SnO2 is confirmed by valence band photoelectron spectrum, whose components show edges at 0, 0.6, and 3.2 eV from Fermi level, respectively. Raman spectroscopy highlights the presence of Sn3O4 (short version of Sn2+2O2Sn4+O2), which confirms the spontaneous formation of this intermediate oxide. It is therefore proposed that an oxidation gradient Sn-SnO-Sn3O4-SnO2 characterizes core-shell system resulting from room temperature Cabrera-Mott oxidation of cluster-assembled nanostructured films.

Gas-phase synthesis of MoO3 nanoclusters with helium-induced high energy (060) crystal facet: Enhancing oxygen adsorption for improved gas-sensing

Adsorbed oxygen species on the surface of metal oxide semiconductors (MOS) play an important role in the field of gas-sensing. However, considering the large number of possible MOS, manipulating surface oxygen species by exposing high-energy crystal facets often requires strict experimental conditions and may not be efficiently repeated for nano MOS. This poses a huge challenge to the rational design of advanced gas-sensing materials. This study explores the fabrication of MoO3 nanocluster (NC) film by cluster beam deposition. Helium (He) is co-fed with argon (Ar) into the aggregation chamber to influence the nucleation and growth of Mo NCs. This unique process facilitated the exposure of the high-energy (060) crystal facet in MoO3 during the aging phase. This exposed crystal facet greatly reduces the oxygen adsorption energy barrier and increases the adsorbed oxygen content, resulting in a significant improvement in gas-sensing performance. The study examined the impact of energetic facets on gas sensor sensitivity by using ethanol, ammonia, and toluene as target gases. The results indicate that exposing high-energy crystal facets significantly enhances sensor performance. This approach to creating NCs with high-energy crystal facets has broad potential for advancing MOS nanostructure-based gas sensors.

Development of Pd/In2O3 hybrid nanoclusters to optimize ethanol vapor sensing.

In this study, we successfully synthesize palladium-decorated indium trioxide (Pd/In2O3) hybrid nanoclusters (NCs) using an advanced dual-target cluster beam deposition (CBD) method, a significant stride in developing high-performance ethanol sensors. The prepared Pd/In2O3 hybrid NCs exhibit exceptional sensitivity, stability, and selectivity to low concentrations of ethanol vapor, with a maximum response value of 101.2 at an optimal operating temperature of 260 °C for 6 at% Pd loading. The dynamic response of the Pd/In2O3-based sensor shows an increase in response with increasing ethanol vapor concentrations within the range of 50 to 1000 ppm. The limit of detection is as low as 24 ppb. The sensor exhibits a high sensitivity of 28.24 ppm-1/2, with response and recovery times of 2.7 and 4.4 seconds, respectively, for 100 ppm ethanol vapor. Additionally, the sensor demonstrates excellent repeatability and stability, with only a minor decrease in response observed over 30 days and notable selectivity for ethanol compared to other common volatile organic compounds. The study highlights the potential of Pd/In2O3 NCs as promising materials for ethanol gas sensors, leveraging the unique capabilities of CBD for controlled synthesis and the catalytic properties of Pd for enhanced gas-sensing performance.

The onset of aerosol Au nanoparticle crystallization: accretion & explosive nucleation.

The crystallization of gold nanoparticles is investigated in the gas-phase by molecular dynamics (MD) that is most relevant to their synthesis by aerosol processes (flame, plasma, or cluster beam deposition). A particle size-dependent metastable region, 200-300 °C wide, is revealed between the melting and freezing points of Au. This region decreases as the MD heating or cooling rates decrease. Two separate stages, subcritical and supercritical cluster formation, are distinguished during isothermal crystallization of 2.5-11 nm Au nanoparticles at 500-1000 K. The degree of Au crystallization (face-centered cubic or hexagonal close-packing) is quantified based on the Au atom local crystalline disorder. The onset of crystallization is identified by the steep rise of the fraction of atoms that retain their crystallinity in the largest subcritical cluster, accompanied by a sharp drop of the amorphous fraction of the Au nanoparticle. Crystallization starts from, at least, one atom layer below the surface of the nanoparticle and then quickly expands to its surface and bulk. Two crystallization nucleation pathways are identified: (a) explosive nucleation well below the Au freezing point resulting in many small and broadly distributed crystals; and (b) accretion nucleation near the freezing point where narrowly distributed and larger crystals are formed that grow by accretion and coalescence. X-ray diffraction (XRD) patterns are generated by MD, from which the dynamics of crystal growth are elucidated, consistent with the literature and in excellent agreement with direct tracing of crystal sizes.

Gas-Phase CuPd Bimetallic Cluster-Modified Electrodes as Model Electrocatalysts for CO2 Conversion

Copper-based electrocatalysts possess the unique ability to convert CO2 to multicarbon products such as ethylene – a precursor in many industrial processes. However, their stability and product selectivity remain insufficient. A promising approach to overcome these shortcomings and design better CO2RR electrocatalysts is to tune Cu selectivity by forming bimetallic Cu-M systems [1] while establishing their detailed structure-selectivity relationship. To achieve this, we used laser ablation Cluster Beam Deposition (CBD) [2] to produce well-defined bimetallic cluster-modified electrodes [2]. More specifically, CuPd clusters with an original average size of 2.5 nm and mass loadings of 1-3 µg cm-2 were deposited onto a carbon support. To produce a model catalyst which allows the independent investigation of the electronic and geometric structural effects induced to Cu by the second element, a Cu0.9Pd0.1 composition was selected [3]. CuPd cluster-decorated electrodes were tested for CO2 electrolysis and methane (C1), and ethylene (C2) were found among the products. Observed from the electrocatalytic activity trends, the evolution of C2 products is correlated with the cluster mass loading. In addition, the cluster coverage has an effect on the onset of the competitive H2 evolution (HER); with the lowest cluster-loaded electrodes presenting more intense HER due to limited cluster coverage of the carbon substrate. High resolution (Scanning) Transmission Electron Microscopy ((S)TEM) coupled with Energy-dispersive X-ray spectroscopy (EDX), and X-ray Photoelectron Spectroscopy (XPS) analyses of the as-prepared cluster-modified electrodes, show that the clusters feature some degree of CuPd alloying in the ambient. CuPd cluster-based systems will then be investigated in-situ using X-ray absorption spectroscopy to unravel their structure-catalytic performance relationship.

Stretchable Electrodes for Medical Devices

[Key topics: ElectrodesElectrodeposition techniquesElectrochemical propertiesStructure – physical properties relationships] The fabrication of electrodes on polymers, and especially on elastomers, is relevant in several fields. Among them, the medical field can benefit a lot from these kinds of electrodes. The human body uses electrical signaling in the muscles as well as in the nervous system to transfer energy and information between the brain and the rest of the body. Cardiac pacemakers, neuromodulation systems, neuromonitoring systems, brain machine interfaces are all examples where electrodes play a key role. Most of the body tissues are soft with unique shapes. When it is required to transfer electrical signals between the soft tissues and hard electronic systems, having soft and conformable interfaces might be particularly advantageous to increase the efficacy of the therapies, the energy consumption of the medical devices and the patient’s quality of life.We have developed several solutions to obtain metal patterns on elastomers that are stretchable, strongly adhered and with high charge-storage capacity. The methods are based on SCBI (Supersonic Cluster Beam Implantation) that allows to form a nanocomposite made of metal nanoparticles embedded in the elastomer, which acts as seed where thin film electrodes are created either through physical vapor techniques or by electro or electroless deposition.Here we compare electrodes made of Pt, Pt-Ir, Ir and IrOx obtained via electrochemical and physical vapor techniques. We present how, by tuning the process parameters, is possible to control the electrodes properties such as the charge-storage capacity, the corrosion under electrical stimulation and stability to tensile and compressive stresses. We show how the electrochemical and mechanical properties are correlated to the micro-structure, the grain morphology, and the stoichiometry. It is also shown how obtaining the electrodes with the right specific surface area is essential to guarantee stability against corrosion under high currents input.

Coordination-induced bond weakening in NiC3: An experimental and theoretical investigation.

Mass-selected photoelectron velocity-map imaging spectroscopy in conjunction with the density functional theory calculations was employed to investigate the geometrical and chemical bonding properties of NiC3-/0. Both the photoelectron spectrum and photoelectron angular distribution were measured from the spectra, yielding useful geometrical and electronic information about NiC3-/0. The complementary theoretical calculations suggest that the linear and fan-like structures were both populated experimentally in the cluster beam. Further comparative study on the synergistic donor-acceptor interactions in both isomers revealed the side-on coordination-induced bond weakening in the fan-like isomer as compared to the linear isomer. These findings will shed light on the structure-dependent reactivity of transition metal carbides.

Improvement of Lipid Detection in Mouse Brain and Human Uterine Tissue Sections Using In Situ Matrix Enhanced Secondary Ion Mass Spectrometry.

The potential of mass spectrometry imaging, and especially ToF-SIMS 2D and 3D imaging, for submicrometer-scale, label-free molecular localization in biological tissues is undisputable. Nevertheless, sensitivity issues remain, especially when one wants to achieve the best lateral and vertical (nanometer-scale) resolution. In this study, the interest of in situ matrix transfer for tissue analysis with cluster ion beams (Bin+, Arn+) is explored in detail, using a series of six low molecular weight acidic (MALDI) matrices. After estimating the sensitivity enhancements for phosphatidylcholine (PC), an abundant lipid type present in almost any kind of cell membrane, the most promising matrices were softly transferred in situ on mouse brain and human uterine tissue samples using a 10 keV Ar3000+ cluster beam. Signal enhancements up to 1 order of magnitude for intact lipid signals were observed in both tissues under Bi5+ and Ar3000+ bombardment. The main findings of this study lie in the in-depth characterization of uterine tissue samples, the demonstration that the transferred matrices also improve signal efficiency in the negative ion polarity and that they perform as well when using Bin+ and Arn+ primary ions for analysis and imaging.

Mass-selected ion-molecule cluster beam apparatus for ultrafast photofragmentation studies.

We describe an apparatus for investigating the excited-state dissociation dynamics of mass-selected ion-molecule clusters by mass-resolving and detecting photofragment-ions and neutrals, in coincidence, using an ultrafast laser operating at high repetition rates. The apparatus comprises a source that generates ion-molecule clusters, a time-of-flight spectrometer, and a mass filter that selects the desired anions, and a linear-plus-quadratic reflectron mass spectrometer that discriminates the fragment anions after the femtosecond laser excites the clusters. The fragment neutrals and anions are then captured by two channeltron detectors. The apparatus performance is tested by measuring the photofragments: I-, CF3I-, and neutrals from photoexcitation of the ion-molecule cluster CF3I·I- using femtosecond UV laser pulses with a wavelength of 266nm. The experimental results are compared with our ground state and excited state electronic structure calculations as well as the existing results and calculations, with particular attention to the generation mechanism of the anion fragments and dissociation channels of the ion-molecule cluster CF3I·I- in the charge-transfer excited state.

A multi-timescale model predicts the spherical-to-cubic morphology crossover of magnetron-sputtered niobium nanoparticles

Sputter-based cluster beam deposition offers a solvent- and effluent-free physical method to synthesize nanoparticles (NPs) with tailored characteristics. Despite the broad capabilities to control the NP architecture via multiple parameters such as magnetron power, gas pressure and flow, type of gas, etc., the technique is still far from being at hand because of insufficient understanding of the processes of NP nucleation, growth, and transport. Here, we synthesize Nb NPs of spherical (diameter 32 nm) and cubic (side length 19 nm) shape, depending on pressure, and perform a detailed structural characterization. A known analytical model of the NP growth and thermalization was modified to account for ion bombardment and non-ideal atomic sticking in the plasma. The model was enforced with ad hoc multi-timescale molecular dynamic simulations to unveil the peculiarities of the growth of Nb NPs and explain the difference in their morphology.

Comparing sputter rates, depth resolution, and ion yields for different gas cluster ion beams (GCIB): A practical guide to choosing the best GCIB for every application

Molecular gas species for gas cluster ion beams (GCIBs), such as carbon dioxide and water, were examined with a range of beam energies and cluster sizes to compare with the “universal relation” of the sputter yield, Y, per cluster atom against incident beam energy, E, per cluster atom of Arn cluster beam using Irganox 1010. In this work, we compare Arn, (CO2)n, and (H2O)n gas clusters to the universal equations for Arn clusters. To discuss molecular gas species for GCIBs, energy per nucleon (E/N) needs to replace energy per atom. We monitored sputter rate, depth resolution, and secondary ion yield as a function of the beam parameters: gas species, beam energy, and cluster size. (H2O)n GCIB shows reduced sputter rates and improved depth resolution with high sensitivity compared to Arn and (CO2)n GCIBs. These initial results indicate the potential to achieve high-depth resolution with high sensitivity and suggest that (H2O)n cluster ion beam has the potential to play a significant role in surface analysis techniques with organic materials. Results also show that no single set of conditions will provide the “best gas cluster ion beam” for all applications. However, it is possible to choose a set of conditions that will be more or less optimal depending on the experimental goals, such as maximizing the sputter rate, depth resolution, and molecular ion yield. In this work, we recommend the following three guidelines for GCIB users to set their own conditions: (1) to maximize the sputter rate, select a smaller cluster (higher E/N), but be aware that this will increase fragmentation and reduce molecular ion yield; (2) to maximize the depth resolution, select a larger cluster (lower E/N), and use (H2O)n GCIB, if possible; and (3) to maximize the molecular ion signal, use the highest beam energy available, and select a cluster with 0.15–0.25 eV/nucleon for Ar and (CO2)n GCIBs or around 0.1 eV/nucleon if using (H2O)n GCIB. These results are valid for XPS, SIMS, and any technique that utilizes GCIBs.

Contrast inversion in neutral-atom microscopy using atomic cluster beams

This work explores the possibility of using atomic cluster beams as a probe for neutral-atom microscopy (NAM) measurements. Using a beam of Kr clusters with mean size $\ensuremath{\sim}{10}^{4}$ atoms/cluster we demonstrate that topographical contrast can be obtained, similar to that in the case of monoatomic beams. Further, using atomically thin films of ${\mathrm{MoS}}_{2}$ grown on ${\mathrm{SiO}}_{2}\text{/}\mathrm{Si}$ substrate we show that NAM imaging using Kr clusters is also possible in domains where topographical contrast is not expected. Surprisingly, these images show an inverted contrast pattern when compared to the case of monoatomic beams. We attempt to understand these observations on the basis of angular distributions resulting from cluster-surface scattering. Finally, we discuss the implications of these results toward achieving a high lateral resolution neutral-atom microscope using atomic cluster beams as probe, with an estimated ultimate achievable lateral resolution up to 20 nm.

A facile way to tune the chemical composition of gas-phase synthesized nanoclusters

Cluster beam deposition (CBD) represents a powerful and versatile gas-phase synthesis method to fabricate nanoclusters that are in demand for various fields. However, the ready control of the chemical composition is of great significance and is still a challenge. In this work, the influences of sputtering power and Ar fluxes on the composition, size and shape of Sm-Co nanoclusters fabricated by the CBD method using a single composite target have been systematically investigated. The chemical composition of nanoclusters has been characterized by high-angle annular dark-field (HAADF) images and EDS of high-resolution transmission electron microscopy. As the sputtering power increases or the Ar fluxes decrease, the Co concentration in nanoclusters gradually increases, the variation of composition in nanoclusters is consistent with the electrocatalytic measurement results. The mechanism by which the composition changes is proposed to be associated with the distinct scattering for Sm and Co by Ar atoms. The composition of nanoclusters can be quantitatively tuned over a wide range by Ar fluxes and sputtering power. We demonstrate an effective way to synthesize nanoclusters with various chemical compositions and manipulate their corresponding functional properties, which advances the design and synthesis of nanoclusters and may be important for both basic research and applications.